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Title: Ultrafast optical snapshots of hybrid perovskites reveal the origin of multiband electronic transitions

Abstract

In this paper, connecting the complex electronic excitations of hybrid perovskites to their intricate organic-inorganic lattice structure has critical implications for energy conversion and optoelectronic technologies. Here we detail the multiband, multivalley electronic structure of a halide hybrid perovskite by measuring the absorption transients of a millimeter-scale-grain thin film as it undergoes a thermally controlled reversible tetragonal-to-orthogonal phase transition. Probing nearly single grains of this hybrid perovskite, we observe an unreported energy splitting (degeneracy lifting) of the high-energy 2.6 eV band in the tetragonal phase that further splits as the rotational degrees of freedom of the disordered CH3NH3+ molecules are reduced when the sample is cooled. This energy splitting drastically increases during an extended phase-transition coexistence region that persists from 160 to 120 K, becoming more pronounced in the orthorhombic phase. By tracking the temperature-dependent optical transition energies and using symmetry analysis that describes the evolution of electronic states from the tetragonal phase to the orthorhombic phase, we assign this energy splitting to the nearly degenerate transitions in the tetragonal phase from both the R- and M-point-derived states. Importantly, these assignments explain how momentum conservation effects lead to long hot-carrier lifetimes in the room-temperature tetragonal phase, with faster hot-carrier relaxationmore » when the hybrid perovskite structurally transitions to the orthorhombic phase due to enhanced scattering at the Γ point.« less

Authors:
 [1];  [2];  [2];  [3];  [2]; ORCiD logo [4]
  1. Brookhaven National Lab. (BNL), Upton, NY (United States). Center for Functional Nanomaterials (CFN); Univ. of Alabama, Birmingham, AL (United States). Dept. of Physics
  2. Los Alamos National Lab. (LANL), Los Alamos, NM (United States)
  3. National Inst. of Applied Sciences (INSA)/CNRS, Rennes (France). Optical Functions for Information Technologies (FOTON)
  4. Brookhaven National Lab. (BNL), Upton, NY (United States). Center for Functional Nanomaterials (CFN)
Publication Date:
Research Org.:
Brookhaven National Lab. (BNL), Upton, NY (United States); Los Alamos National Lab. (LANL), Los Alamos, NM (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22) Scientific User Facilities Division; USDOE National Nuclear Security Administration (NNSA); USDOE Laboratory Directed Research and Development (LDRD) Program; Banque Populaire de l'Ouest Foundation
OSTI Identifier:
1437444
Alternate Identifier(s):
OSTI ID: 1410471; OSTI ID: 1460651
Report Number(s):
BNL-204648-2018-JAAM; LA-UR-17-29873
Journal ID: ISSN 2469-9950; PRBMDO; TRN: US1900329
Grant/Contract Number:  
SC0012704; AC52-06NA25396; 08SPCE973; PEROPHOT 2015
Resource Type:
Accepted Manuscript
Journal Name:
Physical Review B
Additional Journal Information:
Journal Volume: 96; Journal Issue: 19; Journal ID: ISSN 2469-9950
Publisher:
American Physical Society (APS)
Country of Publication:
United States
Language:
English
Subject:
36 MATERIALS SCIENCE; Material Science; Perovskites, electronic structure

Citation Formats

Appavoo, Kannatassen, Nie, Wanyi, Blancon, Jean -Christophe, Even, Jacky, Mohite, Aditya D., and Sfeir, Matthew Y. Ultrafast optical snapshots of hybrid perovskites reveal the origin of multiband electronic transitions. United States: N. p., 2017. Web. doi:10.1103/PhysRevB.96.195308.
Appavoo, Kannatassen, Nie, Wanyi, Blancon, Jean -Christophe, Even, Jacky, Mohite, Aditya D., & Sfeir, Matthew Y. Ultrafast optical snapshots of hybrid perovskites reveal the origin of multiband electronic transitions. United States. doi:10.1103/PhysRevB.96.195308.
Appavoo, Kannatassen, Nie, Wanyi, Blancon, Jean -Christophe, Even, Jacky, Mohite, Aditya D., and Sfeir, Matthew Y. Tue . "Ultrafast optical snapshots of hybrid perovskites reveal the origin of multiband electronic transitions". United States. doi:10.1103/PhysRevB.96.195308. https://www.osti.gov/servlets/purl/1437444.
@article{osti_1437444,
title = {Ultrafast optical snapshots of hybrid perovskites reveal the origin of multiband electronic transitions},
author = {Appavoo, Kannatassen and Nie, Wanyi and Blancon, Jean -Christophe and Even, Jacky and Mohite, Aditya D. and Sfeir, Matthew Y.},
abstractNote = {In this paper, connecting the complex electronic excitations of hybrid perovskites to their intricate organic-inorganic lattice structure has critical implications for energy conversion and optoelectronic technologies. Here we detail the multiband, multivalley electronic structure of a halide hybrid perovskite by measuring the absorption transients of a millimeter-scale-grain thin film as it undergoes a thermally controlled reversible tetragonal-to-orthogonal phase transition. Probing nearly single grains of this hybrid perovskite, we observe an unreported energy splitting (degeneracy lifting) of the high-energy 2.6 eV band in the tetragonal phase that further splits as the rotational degrees of freedom of the disordered CH3NH3+ molecules are reduced when the sample is cooled. This energy splitting drastically increases during an extended phase-transition coexistence region that persists from 160 to 120 K, becoming more pronounced in the orthorhombic phase. By tracking the temperature-dependent optical transition energies and using symmetry analysis that describes the evolution of electronic states from the tetragonal phase to the orthorhombic phase, we assign this energy splitting to the nearly degenerate transitions in the tetragonal phase from both the R- and M-point-derived states. Importantly, these assignments explain how momentum conservation effects lead to long hot-carrier lifetimes in the room-temperature tetragonal phase, with faster hot-carrier relaxation when the hybrid perovskite structurally transitions to the orthorhombic phase due to enhanced scattering at the Γ point.},
doi = {10.1103/PhysRevB.96.195308},
journal = {Physical Review B},
number = 19,
volume = 96,
place = {United States},
year = {2017},
month = {11}
}

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Cited by: 4 works
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Figures / Tables:

Fig. 1 Fig. 1: Steady-state linear optical properties of hybrid organic-inorganic perovskite. (a) Crystal structure of the HOIP in its orthorhombic (low temperature phase, blue) and tetragonal (high temperature phase, red) state. (b) Characteristic linear absorption spectra before, during and after the phase transition. Inset represents spectra taken at all temperature points.more » (c, d) 2D absorption spectra as a function of temperature in the visible and near-infrared spectral regions. Note change of color scale. Region depicting phase-coexistence is marked by white dotted lines.« less

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Works referenced in this record:

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

Metal-halide perovskites for photovoltaic and light-emitting devices
journal, May 2015

  • Stranks, Samuel D.; Snaith, Henry J.
  • Nature Nanotechnology, Vol. 10, Issue 5
  • DOI: 10.1038/nnano.2015.90

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


Rotational dynamics of organic cations in the CH 3 NH 3 PbI 3 perovskite
journal, January 2015

  • Chen, Tianran; Foley, Benjamin J.; Ipek, Bahar
  • Physical Chemistry Chemical Physics, Vol. 17, Issue 46
  • DOI: 10.1039/C5CP05348J

Band filling with free charge carriers in organometal halide perovskites
journal, August 2014


Efficiency of hot‐carrier solar energy converters
journal, May 1982

  • Ross, Robert T.; Nozik, Arthur J.
  • Journal of Applied Physics, Vol. 53, Issue 5
  • DOI: 10.1063/1.331124

Hot-Electron Transfer from Semiconductor Nanocrystals
journal, June 2010


Temperature-Dependent Charge-Carrier Dynamics in CH 3 NH 3 PbI 3 Perovskite Thin Films
journal, September 2015

  • Milot, Rebecca L.; Eperon, Giles E.; Snaith, Henry J.
  • Advanced Functional Materials, Vol. 25, Issue 39
  • DOI: 10.1002/adfm.201502340

Low trap-state density and long carrier diffusion in organolead trihalide perovskite single crystals
journal, January 2015


Measurement of the acoustic-to-optical phonon coupling in multicomponent systems
journal, February 2015


Detection of X-ray photons by solution-processed lead halide perovskites
journal, May 2015

  • Yakunin, Sergii; Sytnyk, Mykhailo; Kriegner, Dominik
  • Nature Photonics, Vol. 9, Issue 7
  • DOI: 10.1038/nphoton.2015.82

Direct measurement of the exciton binding energy and effective masses for charge carriers in organic–inorganic tri-halide perovskites
journal, June 2015

  • Miyata, Atsuhiko; Mitioglu, Anatolie; Plochocka, Paulina
  • Nature Physics, Vol. 11, Issue 7
  • DOI: 10.1038/nphys3357

Interface engineering of highly efficient perovskite solar cells
journal, July 2014


Relativistic GW calculations on CH3NH3PbI3 and CH3NH3SnI3 Perovskites for Solar Cell Applications
journal, March 2014

  • Umari, Paolo; Mosconi, Edoardo; De Angelis, Filippo
  • Scientific Reports, Vol. 4, Issue 1
  • DOI: 10.1038/srep04467

Hybrid Germanium Iodide Perovskite Semiconductors: Active Lone Pairs, Structural Distortions, Direct and Indirect Energy Gaps, and Strong Nonlinear Optical Properties
journal, May 2015

  • Stoumpos, Constantinos C.; Frazer, Laszlo; Clark, Daniel J.
  • Journal of the American Chemical Society, Vol. 137, Issue 21
  • DOI: 10.1021/jacs.5b01025

Growth of CH3NH3PbI3 cuboids with controlled size for high-efficiency perovskite solar cells
journal, August 2014

  • Im, Jeong-Hyeok; Jang, In-Hyuk; Pellet, Norman
  • Nature Nanotechnology, Vol. 9, Issue 11
  • DOI: 10.1038/nnano.2014.181

Lead halide perovskite nanowire lasers with low lasing thresholds and high quality factors
journal, April 2015

  • Zhu, Haiming; Fu, Yongping; Meng, Fei
  • Nature Materials, Vol. 14, Issue 6
  • DOI: 10.1038/nmat4271

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


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

Are Mobilities in Hybrid Organic–Inorganic Halide Perovskites Actually “High”?
journal, November 2015

  • Brenner, Thomas M.; Egger, David A.; Rappe, Andrew M.
  • The Journal of Physical Chemistry Letters, Vol. 6, Issue 23
  • DOI: 10.1021/acs.jpclett.5b02390

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

  • Leguy, Aurélien M. A.; Azarhoosh, Pooya; Alonso, M. Isabel
  • Nanoscale, Vol. 8, Issue 12
  • DOI: 10.1039/C5NR05435D

Size-dependent phase transition in methylammonium lead iodide perovskite microplate crystals
journal, April 2016

  • Li, Dehui; Wang, Gongming; Cheng, Hung-Chieh
  • Nature Communications, Vol. 7, Issue 1
  • DOI: 10.1038/ncomms11330

The Effects of Electronic Impurities and Electron-Hole Recombination Dynamics on Large-Grain Organic-Inorganic Perovskite Photovoltaic Efficiencies
journal, April 2016

  • Blancon, Jean-Christophe; Nie, Wanyi; Neukirch, Amanda J.
  • Advanced Functional Materials, Vol. 26, Issue 24
  • DOI: 10.1002/adfm.201505324

Relativistic quasiparticle self-consistent electronic structure of hybrid halide perovskite photovoltaic absorbers
journal, April 2014


Effect of Carrier Thermalization Dynamics on Light Emission and Amplification in Organometal Halide Perovskites
journal, December 2014

  • Chen, Kai; Barker, Alex J.; Morgan, Francis L. C.
  • The Journal of Physical Chemistry Letters, Vol. 6, Issue 1
  • DOI: 10.1021/jz502528c

Light-activated photocurrent degradation and self-healing in perovskite solar cells
journal, May 2016

  • Nie, Wanyi; Blancon, Jean-Christophe; Neukirch, Amanda J.
  • Nature Communications, Vol. 7, Issue 1
  • DOI: 10.1038/ncomms11574

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


High-efficiency solution-processed perovskite solar cells with millimeter-scale grains
journal, January 2015


Phonon bottleneck in quantum dots: Role of lifetime of the confined optical phonons
journal, February 1999


Size-Dependent Temperature Variation of the Energy Gap in Lead-Salt Quantum Dots
journal, October 1998


Plasmon-induced hot carrier science and technology
journal, January 2015

  • Brongersma, Mark L.; Halas, Naomi J.; Nordlander, Peter
  • Nature Nanotechnology, Vol. 10, Issue 1
  • DOI: 10.1038/nnano.2014.311

Distinguishing between plasmon-induced and photoexcited carriers in a device geometry
journal, July 2015

  • Zheng, Bob Y.; Zhao, Hangqi; Manjavacas, Alejandro
  • Nature Communications, Vol. 6, Issue 1
  • DOI: 10.1038/ncomms8797

Charge carrier recombination channels in the low-temperature phase of organic-inorganic lead halide perovskite thin films
journal, August 2014

  • Wehrenfennig, Christian; Liu, Mingzhen; Snaith, Henry J.
  • APL Materials, Vol. 2, Issue 8
  • DOI: 10.1063/1.4891595

Breaking the Phonon Bottleneck in PbSe and CdSe Quantum Dots: Time-Domain Density Functional Theory of Charge Carrier Relaxation
journal, December 2008

  • Kilina, Svetlana V.; Kilin, Dmitri S.; Prezhdo, Oleg V.
  • ACS Nano, Vol. 3, Issue 1
  • DOI: 10.1021/nn800674n

Thermally Activated Exciton Dissociation and Recombination Control the Carrier Dynamics in Organometal Halide Perovskite
journal, June 2014

  • Savenije, Tom J.; Ponseca, Carlito S.; Kunneman, Lucas
  • The Journal of Physical Chemistry Letters, Vol. 5, Issue 13
  • DOI: 10.1021/jz500858a

Trap States in Lead Iodide Perovskites
journal, January 2015

  • Wu, Xiaoxi; Trinh, M. Tuan; Niesner, Daniel
  • Journal of the American Chemical Society, Vol. 137, Issue 5
  • DOI: 10.1021/ja512833n

Unusual defect physics in CH 3 NH 3 PbI 3 perovskite solar cell absorber
journal, February 2014

  • Yin, Wan-Jian; Shi, Tingting; Yan, Yanfa
  • Applied Physics Letters, Vol. 104, Issue 6
  • DOI: 10.1063/1.4864778

Exciton and Free Charge Dynamics of Methylammonium Lead Iodide Perovskites Are Different in the Tetragonal and Orthorhombic Phases
journal, August 2015

  • Wang, He; Whittaker-Brooks, Luisa; Fleming, Graham R.
  • The Journal of Physical Chemistry C, Vol. 119, Issue 34
  • DOI: 10.1021/acs.jpcc.5b04403

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

  • Azarhoosh, Pooya; McKechnie, Scott; Frost, Jarvist M.
  • APL Materials, Vol. 4, Issue 9
  • DOI: 10.1063/1.4955028

Sequential deposition as a route to high-performance perovskite-sensitized solar cells
journal, July 2013

  • Burschka, Julian; Pellet, Norman; Moon, Soo-Jin
  • Nature, Vol. 499, Issue 7458, p. 316-319
  • DOI: 10.1038/nature12340

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

Organometallic Halide Perovskites: Sharp Optical Absorption Edge and Its Relation to Photovoltaic Performance
journal, March 2014

  • De Wolf, Stefaan; Holovsky, Jakub; Moon, Soo-Jin
  • The Journal of Physical Chemistry Letters, Vol. 5, Issue 6
  • DOI: 10.1021/jz500279b

DFT and k · p modelling of the phase transitions of lead and tin halide perovskites for photovoltaic cells : DFT and
journal, October 2013

  • Even, Jacky; Pedesseau, Laurent; Jancu, Jean-Marc
  • physica status solidi (RRL) - Rapid Research Letters, Vol. 8, Issue 1
  • DOI: 10.1002/pssr.201308183

Observation of Phonon Bottleneck in Quantum Dot Electronic Relaxation
journal, May 2001


Excitons versus free charges in organo-lead tri-halide perovskites
journal, April 2014

  • D’Innocenzo, Valerio; Grancini, Giulia; Alcocer, Marcelo J. P.
  • Nature Communications, Vol. 5, Issue 1
  • DOI: 10.1038/ncomms4586

Analysis of Multivalley and Multibandgap Absorption and Enhancement of Free Carriers Related to Exciton Screening in Hybrid Perovskites
journal, May 2014

  • Even, Jacky; Pedesseau, Laurent; Katan, Claudine
  • The Journal of Physical Chemistry C, Vol. 118, Issue 22
  • DOI: 10.1021/jp503337a

Dual nature of the excited state in organic–inorganic lead halide perovskites
journal, January 2015

  • Stamplecoskie, Kevin G.; Manser, Joseph S.; Kamat, Prashant V.
  • Energy & Environmental Science, Vol. 8, Issue 1
  • DOI: 10.1039/C4EE02988G

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

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


Theory and computation of hot carriers generated by surface plasmon polaritons in noble metals
journal, June 2015

  • Bernardi, Marco; Mustafa, Jamal; Neaton, Jeffrey B.
  • Nature Communications, Vol. 6, Issue 1
  • DOI: 10.1038/ncomms8044

Dynamical Origin of the Rashba Effect in Organohalide Lead Perovskites: A Key to Suppressed Carrier Recombination in Perovskite Solar Cells?
journal, April 2016

  • Etienne, Thibaud; Mosconi, Edoardo; De Angelis, Filippo
  • The Journal of Physical Chemistry Letters, Vol. 7, Issue 9
  • DOI: 10.1021/acs.jpclett.6b00564

Slow Organic-to-Inorganic Sub-Lattice Thermalization in Methylammonium Lead Halide Perovskites Observed by Ultrafast Photoluminescence
journal, May 2016

  • Chang, Angela Y.; Cho, Yi-Ju; Chen, Kuan-Chen
  • Advanced Energy Materials, Vol. 6, Issue 15
  • DOI: 10.1002/aenm.201600422

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

  • Leguy, Aurelien M. A.; Frost, Jarvist Moore; McMahon, Andrew P.
  • Nature Communications, Vol. 6, Issue 1
  • DOI: 10.1038/ncomms8124

Characterization of plasmonic hole arrays as transparent electrical contacts for organic photovoltaics using high-brightness Fourier transform methods
journal, May 2014


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


Optical properties of the organic-inorganic hybrid perovskite C H 3 N H 3 Pb I 3 : Theory and experiment
journal, August 2016


Characterization of an abnormal photoluminescence behavior upon crystal-phase transition of perovskite CH 3 NH 3 PbI 3
journal, January 2015

  • Kong, Weiguang; Ye, Zhenyu; Qi, Zhen
  • Physical Chemistry Chemical Physics, Vol. 17, Issue 25
  • DOI: 10.1039/C5CP02605A

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

Filterless narrowband visible photodetectors
journal, September 2015


Solid-State Physics Perspective on Hybrid Perovskite Semiconductors
journal, April 2015

  • Even, Jacky; Pedesseau, Laurent; Katan, Claudine
  • The Journal of Physical Chemistry C, Vol. 119, Issue 19
  • DOI: 10.1021/acs.jpcc.5b00695

Electronic structure and optical properties of PbS and PbSe quantum dots
journal, January 1997

  • Kang, Inuk; Wise, Frank W.
  • Journal of the Optical Society of America B, Vol. 14, Issue 7
  • DOI: 10.1364/JOSAB.14.001632

Temperature dependence of the direct gap of Si and Ge
journal, April 1983


Temperature dependence of the energy gap in semiconductors
journal, January 1967


Photodetection with Active Optical Antennas
journal, May 2011

  • Knight, M. W.; Sobhani, H.; Nordlander, P.
  • Science, Vol. 332, Issue 6030, p. 702-704
  • DOI: 10.1126/science.1203056

Perovskites: The Emergence of a New Era for Low-Cost, High-Efficiency Solar Cells
journal, October 2013

  • Snaith, Henry J.
  • The Journal of Physical Chemistry Letters, Vol. 4, Issue 21, p. 3623-3630
  • DOI: 10.1021/jz4020162

Optical Transitions in Hybrid Perovskite Solar Cells: Ellipsometry, Density Functional Theory, and Quantum Efficiency Analyses for CH 3 NH 3 PbI 3
journal, January 2016


Giant Rashba Splitting in CH 3 NH 3 PbBr 3 Organic-Inorganic Perovskite
journal, September 2016


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


    Works referencing / citing this record:

    Ultrahigh phase transition temperature in a metal–halide perovskite-type material containing unprecedented hydrogen bonding interactions
    journal, January 2019

    • Hua, Xiu-Ni; Gao, Ji-Xing; Chen, Xiao-Gang
    • Dalton Transactions, Vol. 48, Issue 19
    • DOI: 10.1039/c9dt00945k

    Homogenized halides and alkali cation segregation in alloyed organic-inorganic perovskites
    journal, February 2019

    • Correa-Baena, Juan-Pablo; Luo, Yanqi; Brenner, Thomas M.
    • Science, Vol. 363, Issue 6427
    • DOI: 10.1126/science.aah5065

    Ultrahigh phase transition temperature in a metal–halide perovskite-type material containing unprecedented hydrogen bonding interactions
    journal, January 2019

    • Hua, Xiu-Ni; Gao, Ji-Xing; Chen, Xiao-Gang
    • Dalton Transactions, Vol. 48, Issue 19
    • DOI: 10.1039/c9dt00945k

    Homogenized halides and alkali cation segregation in alloyed organic-inorganic perovskites
    journal, February 2019

    • Correa-Baena, Juan-Pablo; Luo, Yanqi; Brenner, Thomas M.
    • Science, Vol. 363, Issue 6427
    • DOI: 10.1126/science.aah5065

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