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Title: Ultrafast exciton many-body interactions and hot-phonon bottleneck in colloidal cesium lead halide perovskite nanocrystals

Abstract

Defect-tolerant perovskite nanocrystals of the general formula Cs-Pb-X 3 (where X=Cl, Br, and I) have shown exceptional potential in fundamental physics as well as in novel optoelectronic applications as the next generation of solar cells. Although exciton many-body interactions such as biexciton Stark shift, state filling, and Auger recombination are studied extensively, other important correlated effects, such as band gap renormalization (BGR) and hot-phonon bottleneck, are not explored in these nanocrystals. Here we experimentally demonstrate the carrier density dependence of the BGR and an effective hot-phonon bottleneck in CsPb(Cl 0.20Br 0.80) 3 mixed-halide nanocrystals. The results are compared with two other halide compositions, namely, CsPbBr 3 and CsPb(Br 0.55I 0.45) 3 nanocrystals with varying band gaps. The optical response of the nanocrystals changes dramatically across the spectral range of many hundreds of meV at high carrier density due to large BGR. We have calculated the BGR constant ~(6.0+/-0.3) x 10 -8eV cm for CsPb(Cl 0.20Br 0.80) 3 nanocrystals that provides the amount of band gap shift as a function of carrier density. In these nanocrystals, an efficient hot-phonon bottleneck is observed at a carrier density of 3.1 x 10 17cm -3 that slows down the thermalization by 1 order ofmore » magnitude. Our findings reveal that the complex kinetic profile of the exciton dynamics can be analyzed by the global target analysis using the sequential model with increasing lifetimes.« less

Authors:
 [1];  [1];  [2];  [1];  [2];  [3];  [2];  [1]
  1. Indian Inst. of Science Education and Research, Bhopal (India)
  2. Indian Inst. of Science Education and Research, Pune (India)
  3. National Renewable Energy Lab. (NREL), Golden, CO (United States)
Publication Date:
Research Org.:
Energy Frontier Research Centers (EFRC) (United States). Center for Hybrid Organic-Inorganic Semiconductors for Energy (CHOISE); National Renewable Energy Lab. (NREL), Golden, CO (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)
OSTI Identifier:
1476250
Alternate Identifier(s):
OSTI ID: 1469258
Report Number(s):
NREL/JA-5900-72530
Journal ID: ISSN 2469-9950; PRBMDO
Grant/Contract Number:  
AC36-08GO28308
Resource Type:
Accepted Manuscript
Journal Name:
Physical Review B
Additional Journal Information:
Journal Volume: 98; Journal Issue: 11; Journal ID: ISSN 2469-9950
Publisher:
American Physical Society (APS)
Country of Publication:
United States
Language:
English
Subject:
14 SOLAR ENERGY; 75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND SUPERFLUIDITY; excitons; ultrafast phenomena

Citation Formats

Mondal, Anirban, Aneesh, J., Kumar Ravi, Vikash, Sharma, Rituraj, Mir, Wasim J., Beard, Mathew C., Nag, Angshuman, and Adarsh, K. V. Ultrafast exciton many-body interactions and hot-phonon bottleneck in colloidal cesium lead halide perovskite nanocrystals. United States: N. p., 2018. Web. doi:10.1103/PhysRevB.98.115418.
Mondal, Anirban, Aneesh, J., Kumar Ravi, Vikash, Sharma, Rituraj, Mir, Wasim J., Beard, Mathew C., Nag, Angshuman, & Adarsh, K. V. Ultrafast exciton many-body interactions and hot-phonon bottleneck in colloidal cesium lead halide perovskite nanocrystals. United States. doi:10.1103/PhysRevB.98.115418.
Mondal, Anirban, Aneesh, J., Kumar Ravi, Vikash, Sharma, Rituraj, Mir, Wasim J., Beard, Mathew C., Nag, Angshuman, and Adarsh, K. V. Mon . "Ultrafast exciton many-body interactions and hot-phonon bottleneck in colloidal cesium lead halide perovskite nanocrystals". United States. doi:10.1103/PhysRevB.98.115418. https://www.osti.gov/servlets/purl/1476250.
@article{osti_1476250,
title = {Ultrafast exciton many-body interactions and hot-phonon bottleneck in colloidal cesium lead halide perovskite nanocrystals},
author = {Mondal, Anirban and Aneesh, J. and Kumar Ravi, Vikash and Sharma, Rituraj and Mir, Wasim J. and Beard, Mathew C. and Nag, Angshuman and Adarsh, K. V.},
abstractNote = {Defect-tolerant perovskite nanocrystals of the general formula Cs-Pb-X3 (where X=Cl, Br, and I) have shown exceptional potential in fundamental physics as well as in novel optoelectronic applications as the next generation of solar cells. Although exciton many-body interactions such as biexciton Stark shift, state filling, and Auger recombination are studied extensively, other important correlated effects, such as band gap renormalization (BGR) and hot-phonon bottleneck, are not explored in these nanocrystals. Here we experimentally demonstrate the carrier density dependence of the BGR and an effective hot-phonon bottleneck in CsPb(Cl0.20Br0.80)3 mixed-halide nanocrystals. The results are compared with two other halide compositions, namely, CsPbBr3 and CsPb(Br0.55I0.45)3 nanocrystals with varying band gaps. The optical response of the nanocrystals changes dramatically across the spectral range of many hundreds of meV at high carrier density due to large BGR. We have calculated the BGR constant ~(6.0+/-0.3) x 10-8eV cm for CsPb(Cl0.20Br0.80)3 nanocrystals that provides the amount of band gap shift as a function of carrier density. In these nanocrystals, an efficient hot-phonon bottleneck is observed at a carrier density of 3.1 x 1017cm-3 that slows down the thermalization by 1 order of magnitude. Our findings reveal that the complex kinetic profile of the exciton dynamics can be analyzed by the global target analysis using the sequential model with increasing lifetimes.},
doi = {10.1103/PhysRevB.98.115418},
journal = {Physical Review B},
number = 11,
volume = 98,
place = {United States},
year = {2018},
month = {9}
}

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Works referenced in this record:

Intriguing Optoelectronic Properties of Metal Halide Perovskites
journal, June 2016


Efficient Biexciton Interaction in Perovskite Quantum Dots Under Weak and Strong Confinement
journal, September 2016


Beyond Colloidal Cesium Lead Halide Perovskite Nanocrystals: Analogous Metal Halides and Doping
journal, April 2017


Carrier effects on the excitonic absorption in GaAs quantum-well structures: Phase-space filling
journal, September 1990


Spectral and Dynamical Properties of Single Excitons, Biexcitons, and Trions in Cesium–Lead-Halide Perovskite Quantum Dots
journal, March 2016


Highly Stable Cesium Lead Halide Perovskite Nanocrystals through in Situ Lead Halide Inorganic Passivation
journal, August 2017


Band Edge Energies and Excitonic Transition Probabilities of Colloidal CsPbX 3 (X = Cl, Br, I) Perovskite Nanocrystals
journal, September 2016


Measurement of Emission Lifetime Dynamics and Biexciton Emission Quantum Yield of Individual InAs Colloidal Nanocrystals
journal, November 2014

  • Bischof, Thomas S.; Correa, Raoul E.; Rosenberg, Danna
  • Nano Letters, Vol. 14, Issue 12
  • DOI: 10.1021/nl502180w

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


Cation-Induced Band-Gap Tuning in Organohalide Perovskites: Interplay of Spin–Orbit Coupling and Octahedra Tilting
journal, May 2014

  • Amat, Anna; Mosconi, Edoardo; Ronca, Enrico
  • Nano Letters, Vol. 14, Issue 6
  • DOI: 10.1021/nl5012992

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

Iodide management in formamidinium-lead-halide–based perovskite layers for efficient solar cells
journal, June 2017


Quantization of Multiparticle Auger Rates in Semiconductor Quantum Dots
journal, February 2000


Quantum Dot Light-Emitting Diodes Based on Inorganic Perovskite Cesium Lead Halides (CsPbX 3 )
journal, October 2015


Strong interlayer coupling mediated giant two-photon absorption in MoS e 2 /graphene oxide heterostructure: Quenching of exciton bands
journal, April 2016


Tuning the Optical Properties of Cesium Lead Halide Perovskite Nanocrystals by Anion Exchange Reactions
journal, August 2015

  • Akkerman, Quinten A.; D’Innocenzo, Valerio; Accornero, Sara
  • Journal of the American Chemical Society, Vol. 137, Issue 32
  • DOI: 10.1021/jacs.5b05602

Terahertz Conductivity within Colloidal CsPbBr 3 Perovskite Nanocrystals: Remarkably High Carrier Mobilities and Large Diffusion Lengths
journal, July 2016


Screening of hot-carrier relaxation in highly photoexcited semiconductors
journal, February 1981


Low-threshold amplified spontaneous emission and lasing from colloidal nanocrystals of caesium lead halide perovskites
journal, August 2015

  • Yakunin, Sergii; Protesescu, Loredana; Krieg, Franziska
  • Nature Communications, Vol. 6, Issue 1
  • DOI: 10.1038/ncomms9056

Ultrafast Interfacial Electron and Hole Transfer from CsPbBr 3 Perovskite Quantum Dots
journal, September 2015

  • Wu, Kaifeng; Liang, Guijie; Shang, Qiongyi
  • Journal of the American Chemical Society, Vol. 137, Issue 40
  • DOI: 10.1021/jacs.5b08520

Re-examination of the Size-Dependent Absorption Properties of CdSe Quantum Dots
journal, October 2009

  • Jasieniak, Jacek; Smith, Lisa; van Embden, Joel
  • The Journal of Physical Chemistry C, Vol. 113, Issue 45
  • DOI: 10.1021/jp906827m

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


Exciton versus Free Carrier Photogeneration in Organometal Trihalide Perovskites Probed by Broadband Ultrafast Polarization Memory Dynamics
journal, March 2015


Acoustic-optical phonon up-conversion and hot-phonon bottleneck in lead-halide perovskites
journal, January 2017

  • Yang, Jianfeng; Wen, Xiaoming; Xia, Hongze
  • Nature Communications, Vol. 8, Issue 1
  • DOI: 10.1038/ncomms14120

Ultrafast photoinduced dynamics of the organolead trihalide perovskite CH 3 NH 3 PbI 3 on mesoporous TiO 2 scaffolds in the 320–920 nm range
journal, January 2015

  • Flender, Oliver; Klein, Johannes R.; Lenzer, Thomas
  • Physical Chemistry Chemical Physics, Vol. 17, Issue 29
  • DOI: 10.1039/C5CP01973G

Unique Properties of Halide Perovskites as Possible Origins of the Superior Solar Cell Performance
journal, May 2014


Colloidal CsPbBr 3 Perovskite Nanocrystals: Luminescence beyond Traditional Quantum Dots
journal, November 2015

  • Swarnkar, Abhishek; Chulliyil, Ramya; Ravi, Vikash Kumar
  • Angewandte Chemie International Edition, Vol. 54, Issue 51
  • DOI: 10.1002/anie.201508276

Unraveling the Structure and Dynamics of Excitons in Semiconductor Quantum Dots
journal, January 2011

  • Kambhampati, Patanjali
  • Accounts of Chemical Research, Vol. 44, Issue 1
  • DOI: 10.1021/ar1000428

Long-Lived Hot Carriers in Formamidinium Lead Iodide Nanocrystals
journal, May 2017

  • Papagiorgis, Paris; Protesescu, Loredana; Kovalenko, Maksym V.
  • The Journal of Physical Chemistry C, Vol. 121, Issue 22
  • DOI: 10.1021/acs.jpcc.7b02308

Quantum dot-induced phase stabilization of  -CsPbI3 perovskite for high-efficiency photovoltaics
journal, October 2016


Intensity of Optical Absorption by Excitons
journal, December 1957


Complete ultrafast charge carrier dynamics in photo-excited all-inorganic perovskite nanocrystals (CsPbX 3 )
journal, January 2017


Ultrafast Exciton Dynamics in Colloidal CsPbBr 3 Perovskite Nanocrystals: Biexciton Effect and Auger Recombination
journal, February 2017

  • Aneesh, J.; Swarnkar, Abhishek; Kumar Ravi, Vikash
  • The Journal of Physical Chemistry C, Vol. 121, Issue 8
  • DOI: 10.1021/acs.jpcc.7b00762

Biexciton effects in femtosecond nonlinear transmission of semiconductor quantum dots
journal, September 1994


Nanocrystals of Cesium Lead Halide Perovskites (CsPbX 3 , X = Cl, Br, and I): Novel Optoelectronic Materials Showing Bright Emission with Wide Color Gamut
journal, February 2015

  • Protesescu, Loredana; Yakunin, Sergii; Bodnarchuk, Maryna I.
  • Nano Letters, Vol. 15, Issue 6
  • DOI: 10.1021/nl5048779

Structure-Tuned Lead Halide Perovskite Nanocrystals
journal, November 2015

  • Hassan, Yasser; Song, Yin; Pensack, Ryan D.
  • Advanced Materials, Vol. 28, Issue 3
  • DOI: 10.1002/adma.201503461

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