Electron–Hole Correlations Govern Auger Recombination in Nanostructures
Abstract
The fast nonradiative decay of multiexcitonic states via Auger recombination is a fundamental process affecting a variety of applications based on semiconductor nanostructures. From a theoretical perspective, the description of Auger recombination in confined semiconductor nanostructures is a challenging task due to the large number of valence electrons and exponentially growing number of excited excitonic and biexcitonic states that are coupled by the Coulomb interaction. These challenges have restricted the treatment of Auger recombination to simple, noninteracting electron–hole models. Herein we present a novel approach for calculating Auger recombination lifetimes in confined nanostructures having thousands to tens of thousands of electrons, explicitly including electron–hole interactions. We demonstrate that the inclusion of electron–hole correlations are imperative to capture the correct scaling of the Auger recombination lifetime with the size and shape of the nanostructure. In addition, correlation effects are required to obtain quantitatively accurate lifetimes even for systems smaller than the exciton Bohr radius. Neglecting such correlations can result in lifetimes that are two orders of magnitude too long. We establish the utility of the new approach for CdSe quantum dots of varying sizes and for CdSe nanorods of varying diameters and lengths. Our new approach is the first theoretical methodmore »
- Authors:
-
- Univ. of California, Berkeley, CA (United States). Dept. of Chemistry
- Univ. of California, Berkeley, CA (United States). Dept. of Chemistry; Tel Aviv Univ., Ramat Aviv (Israel). The Sackler Center for Computational Molecular and Materials Science; Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States). Materials Science Division
- Publication Date:
- Research Org.:
- Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States). National Energy Research Scientific Computing Center (NERSC); Univ. of California, Oakland, CA (United States)
- Sponsoring Org.:
- USDOE Office of Science (SC)
- OSTI Identifier:
- 1543688
- Grant/Contract Number:
- AC02-05CH11231
- Resource Type:
- Accepted Manuscript
- Journal Name:
- Nano Letters
- Additional Journal Information:
- Journal Volume: 18; Journal Issue: 12; Journal ID: ISSN 1530-6984
- Publisher:
- American Chemical Society
- Country of Publication:
- United States
- Language:
- English
- Subject:
- 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; Chemistry; Science & Technology - Other Topics; Materials Science; Physics
Citation Formats
Philbin, John P., and Rabani, Eran. Electron–Hole Correlations Govern Auger Recombination in Nanostructures. United States: N. p., 2018.
Web. doi:10.1021/acs.nanolett.8b03715.
Philbin, John P., & Rabani, Eran. Electron–Hole Correlations Govern Auger Recombination in Nanostructures. United States. https://doi.org/10.1021/acs.nanolett.8b03715
Philbin, John P., and Rabani, Eran. Wed .
"Electron–Hole Correlations Govern Auger Recombination in Nanostructures". United States. https://doi.org/10.1021/acs.nanolett.8b03715. https://www.osti.gov/servlets/purl/1543688.
@article{osti_1543688,
title = {Electron–Hole Correlations Govern Auger Recombination in Nanostructures},
author = {Philbin, John P. and Rabani, Eran},
abstractNote = {The fast nonradiative decay of multiexcitonic states via Auger recombination is a fundamental process affecting a variety of applications based on semiconductor nanostructures. From a theoretical perspective, the description of Auger recombination in confined semiconductor nanostructures is a challenging task due to the large number of valence electrons and exponentially growing number of excited excitonic and biexcitonic states that are coupled by the Coulomb interaction. These challenges have restricted the treatment of Auger recombination to simple, noninteracting electron–hole models. Herein we present a novel approach for calculating Auger recombination lifetimes in confined nanostructures having thousands to tens of thousands of electrons, explicitly including electron–hole interactions. We demonstrate that the inclusion of electron–hole correlations are imperative to capture the correct scaling of the Auger recombination lifetime with the size and shape of the nanostructure. In addition, correlation effects are required to obtain quantitatively accurate lifetimes even for systems smaller than the exciton Bohr radius. Neglecting such correlations can result in lifetimes that are two orders of magnitude too long. We establish the utility of the new approach for CdSe quantum dots of varying sizes and for CdSe nanorods of varying diameters and lengths. Our new approach is the first theoretical method to postdict the experimentally known “universal volume scaling law” for quantum dots and makes novel predictions for the scaling of the Auger recombination lifetimes in nanorods.},
doi = {10.1021/acs.nanolett.8b03715},
journal = {Nano Letters},
number = 12,
volume = 18,
place = {United States},
year = {2018},
month = {11}
}
Web of Science
Works referenced in this record:
Quantization of Multiparticle Auger Rates in Semiconductor Quantum Dots
journal, February 2000
- Klimov, V. I.
- Science, Vol. 287, Issue 5455
Multicarrier Interactions in Semiconductor Nanocrystals in Relation to the Phenomena of Auger Recombination and Carrier Multiplication
journal, March 2014
- Klimov, Victor I.
- Annual Review of Condensed Matter Physics, Vol. 5, Issue 1
Light-emitting diodes made from cadmium selenide nanocrystals and a semiconducting polymer
journal, August 1994
- Colvin, V. L.; Schlamp, M. C.; Alivisatos, A. P.
- Nature, Vol. 370, Issue 6488
Quantum correlation among photons from a single quantum dot at room temperature
journal, August 2000
- Michler, P.; Imamoğlu, A.; Mason, M. D.
- Nature, Vol. 406, Issue 6799
Evidence for Barrierless Auger Recombination in PbSe Nanocrystals: A Pressure-Dependent Study of Transient Optical Absorption
journal, November 2008
- Pietryga, Jeffrey M.; Zhuravlev, Kirill K.; Whitehead, Michael
- Physical Review Letters, Vol. 101, Issue 21
Controlled Alloying of the Core–Shell Interface in CdSe/CdS Quantum Dots for Suppression of Auger Recombination
journal, April 2013
- Bae, Wan Ki; Padilha, Lazaro A.; Park, Young-Shin
- ACS Nano, Vol. 7, Issue 4
The role of Auger recombination in the temperature-dependent output characteristics (T0=∞) of p-doped 1.3 μm quantum dot lasers
journal, November 2004
- Fathpour, S.; Mi, Z.; Bhattacharya, P.
- Applied Physics Letters, Vol. 85, Issue 22
Colloidal Quantum-Dot Photodetectors Exploiting Multiexciton Generation
journal, June 2009
- Sukhovatkin, V.; Hinds, S.; Brzozowski, L.
- Science, Vol. 324, Issue 5934
Biexciton Quantum Yield of Single Semiconductor Nanocrystals from Photon Statistics
journal, March 2011
- Nair, Gautham; Zhao, Jing; Bawendi, Moungi G.
- Nano Letters, Vol. 11, Issue 3
Charge Carrier Dynamics in Photocatalytic Hybrid Semiconductor–Metal Nanorods: Crossover from Auger Recombination to Charge Transfer
journal, July 2018
- Ben-Shahar, Yuval; Philbin, John P.; Scotognella, Francesco
- Nano Letters, Vol. 18, Issue 8
Universal Size-Dependent Trend in Auger Recombination in Direct-Gap and Indirect-Gap Semiconductor Nanocrystals
journal, May 2009
- Robel, István; Gresback, Ryan; Kortshagen, Uwe
- Physical Review Letters, Vol. 102, Issue 17, Article No. 177404
Suppressed Auger Recombination in “Giant” Nanocrystals Boosts Optical Gain Performance
journal, October 2009
- García-Santamaría, Florencio; Chen, Yongfen; Vela, Javier
- Nano Letters, Vol. 9, Issue 10
(Multi)exciton Dynamics and Exciton Polarizability in Colloidal InAs Quantum Dots
journal, March 2010
- Pijpers, Joep J. H.; Milder, Maaike T. W.; Delerue, Christophe
- The Journal of Physical Chemistry C, Vol. 114, Issue 14
Auger ionization of semiconductor quantum drops in a glass matrix
journal, October 1990
- Chepic, D. I.; Efros, Al. L.; Ekimov, A. I.
- Journal of Luminescence, Vol. 47, Issue 3, p. 113-127
Nonradiative Auger Recombination in Semiconductor Nanocrystals
journal, February 2015
- Vaxenburg, Roman; Rodina, Anna; Shabaev, Andrew
- Nano Letters, Vol. 15, Issue 3
Biexciton Auger Recombination in CdSe/CdS Core/Shell Semiconductor Nanocrystals
journal, March 2016
- Vaxenburg, Roman; Rodina, Anna; Lifshitz, Efrat
- Nano Letters, Vol. 16, Issue 4
Suppression of Auger Processes in Confined Structures
journal, January 2010
- Cragg, George E.; Efros, Alexander L.
- Nano Letters, Vol. 10, Issue 1
Suppression of Biexciton Auger Recombination in CdSe/CdS Dot/Rods: Role of the Electronic Structure in the Carrier Dynamics
journal, August 2010
- Zavelani-Rossi, Margherita; Lupo, Maria Grazia; Tassone, Francesco
- Nano Letters, Vol. 10, Issue 8
Breakdown of Volume Scaling in Auger Recombination in CdSe/CdS Heteronanocrystals: The Role of the Core−Shell Interface
journal, February 2011
- García-Santamaría, Florencio; Brovelli, Sergio; Viswanatha, Ranjani
- Nano Letters, Vol. 11, Issue 2
Effect of the Core/Shell Interface on Auger Recombination Evaluated by Single-Quantum-Dot Spectroscopy
journal, January 2014
- Park, Young-Shin; Bae, Wan Ki; Padilha, Lazaro A.
- Nano Letters, Vol. 14, Issue 2
Atomistic Design of CdSe/CdS Core–Shell Quantum Dots with Suppressed Auger Recombination
journal, September 2016
- Jain, Ankit; Voznyy, Oleksandr; Hoogland, Sjoerd
- Nano Letters, Vol. 16, Issue 10
Ultrafast Carrier Trapping in Thick-Shell Colloidal Quantum Dots
journal, June 2017
- Jain, Ankit; Voznyy, Oleksandr; Korkusinski, Marek
- The Journal of Physical Chemistry Letters, Vol. 8, Issue 14
Effect of Zero- to One-Dimensional Transformation on Multiparticle Auger Recombination in Semiconductor Quantum Rods
journal, November 2003
- Htoon, H.; Hollingsworth, J. A.; Dickerson, R.
- Physical Review Letters, Vol. 91, Issue 22
Quantized Auger recombination of biexcitons in CdSe nanorods studied by time-resolved photoluminescence and transient-absorption spectroscopy
journal, April 2011
- Taguchi, Seiji; Saruyama, Masaki; Teranishi, Toshiharu
- Physical Review B, Vol. 83, Issue 15
Enhanced Multiple Exciton Dissociation from CdSe Quantum Rods: The Effect of Nanocrystal Shape
journal, June 2012
- Zhu, Haiming; Lian, Tianquan
- Journal of the American Chemical Society, Vol. 134, Issue 27
Exciton Relaxation in PbSe Nanorods
journal, August 2012
- Yang, Jun; Hyun, Byung-Ryool; Basile, Anthony J.
- ACS Nano, Vol. 6, Issue 9
Aspect Ratio Dependence of Auger Recombination and Carrier Multiplication in PbSe Nanorods
journal, February 2013
- Padilha, Lazaro A.; Stewart, John T.; Sandberg, Richard L.
- Nano Letters, Vol. 13, Issue 3
Cooling and Auger Recombination of Charges in PbSe Nanorods: Crossover from Cubic to Bimolecular Decay
journal, August 2013
- Aerts, Michiel; Spoor, Frank C. M.; Grozema, Ferdinand C.
- Nano Letters, Vol. 13, Issue 9
Red, Yellow, Green, and Blue Amplified Spontaneous Emission and Lasing Using Colloidal CdSe Nanoplatelets
journal, September 2015
- She, Chunxing; Fedin, Igor; Dolzhnikov, Dmitriy S.
- ACS Nano, Vol. 9, Issue 10
Efficient Carrier Multiplication in Colloidal Silicon Nanorods
journal, August 2017
- Stolle, Carl Jackson; Lu, Xiaotang; Yu, Yixuan
- Nano Letters, Vol. 17, Issue 9
Area- and Thickness-Dependent Biexciton Auger Recombination in Colloidal CdSe Nanoplatelets: Breaking the “Universal Volume Scaling Law”
journal, April 2017
- Li, Qiuyang; Lian, Tianquan
- Nano Letters, Vol. 17, Issue 5
Auger recombination of excitons in one-dimensional systems
journal, June 2006
- Wang, Feng; Wu, Yang; Hybertsen, Mark S.
- Physical Review B, Vol. 73, Issue 24
Pseudopotential Theory of Auger Processes in CdSe Quantum Dots
journal, July 2003
- Wang, Lin-Wang; Califano, Marco; Zunger, Alex
- Physical Review Letters, Vol. 91, Issue 5
Theory of highly excited semiconductor nanostructures including Auger coupling: Exciton-biexciton mixing in CdSe nanocrystals
journal, October 2011
- Korkusinski, Marek; Voznyy, Oleksandr; Hawrylak, Pawel
- Physical Review B, Vol. 84, Issue 15
Trion, biexciton, and exciton dynamics in single self-assembled CdSe quantum dots
journal, September 2003
- Patton, B.; Langbein, W.; Woggon, U.
- Physical Review B, Vol. 68, Issue 12
Effect of Thermal Fluctuations on the Radiative Rate in Core/Shell Quantum Dots
journal, February 2017
- Balan, Arunima D.; Eshet, Hagai; Olshansky, Jacob H.
- Nano Letters, Vol. 17, Issue 3
Origins of Singlet Fission in Solid Pentacene from an ab initio Green’s Function Approach
journal, December 2017
- Refaely-Abramson, Sivan; da Jornada, Felipe H.; Louie, Steven G.
- Physical Review Letters, Vol. 119, Issue 26
Electron-hole excitations and optical spectra from first principles
journal, August 2000
- Rohlfing, Michael; Louie, Steven G.
- Physical Review B, Vol. 62, Issue 8
The Electronic Structure of CdSe/CdS Core/Shell Seeded Nanorods: Type-I or Quasi-Type-II?
journal, November 2013
- Eshet, Hagai; Grünwald, Michael; Rabani, Eran
- Nano Letters, Vol. 13, Issue 12
Size-Dependent Valence and Conduction Band-Edge Energies of Semiconductor Nanocrystals
journal, June 2011
- Jasieniak, Jacek; Califano, Marco; Watkins, Scott E.
- ACS Nano, Vol. 5, Issue 7
Direct Pseudopotential Calculation of Exciton Coulomb and Exchange Energies in Semiconductor Quantum Dots
journal, February 1997
- Franceschetti, Alberto; Zunger, Alex
- Physical Review Letters, Vol. 78, Issue 5
Electronic Structure Pseudopotential Calculations of Large (.apprx.1000 Atoms) Si Quantum Dots
journal, February 1994
- Wang, Lin Wang; Zunger, Alex
- The Journal of Physical Chemistry, Vol. 98, Issue 8
Pseudopotential calculations of nanoscale CdSe quantum dots
journal, April 1996
- Wang, Lin-Wang; Zunger, Alex
- Physical Review B, Vol. 53, Issue 15
Electronic properties of CdSe nanocrystals in the absence and presence of a dielectric medium
journal, March 1999
- Rabani, Eran; Hetényi, Balázs; Berne, B. J.
- The Journal of Chemical Physics, Vol. 110, Issue 11
Pseudopotential study of electron-hole excitations in colloidal free-standing InAs quantum dots
journal, January 2000
- Williamson, A. J.; Zunger, Alex
- Physical Review B, Vol. 61, Issue 3
Extraction, through filter‐diagonalization, of general quantum eigenvalues or classical normal mode frequencies from a small number of residues or a short‐time segment of a signal. I. Theory and application to a quantum‐dynamics model
journal, May 1995
- Wall, Michael R.; Neuhauser, Daniel
- The Journal of Chemical Physics, Vol. 102, Issue 20
Very Large Electronic Structure Calculations Using an Out-of-Core Filter-Diagonalization Method
journal, July 2002
- Toledo, Sivan; Rabani, Eran
- Journal of Computational Physics, Vol. 180, Issue 1
1D Exciton Spectroscopy of Semiconductor Nanorods
journal, October 2004
- Shabaev, A.; Efros, Al. L.
- Nano Letters, Vol. 4, Issue 10
Size-Dependent Trap-Assisted Auger Recombination in Semiconductor Nanocrystals
journal, March 2013
- Cohn, Alicia W.; Schimpf, Alina M.; Gunthardt, Carolyn E.
- Nano Letters, Vol. 13, Issue 4
Theory of multiexciton generation in semiconductor nanocrystals
journal, August 2010
- Rabani, Eran; Baer, Roi
- Chemical Physics Letters, Vol. 496, Issue 4-6
Expeditious Stochastic Calculation of Multiexciton Generation Rates in Semiconductor Nanocrystals
journal, January 2012
- Baer, Roi; Rabani, Eran
- Nano Letters, Vol. 12, Issue 4
Enhanced Multiple Exciton Generation in Quasi-One-Dimensional Semiconductors
journal, August 2011
- Cunningham, Paul D.; Boercker, Janice E.; Foos, Edward E.
- Nano Letters, Vol. 11, Issue 8
Multiexciton Dynamics in Infrared-Emitting Colloidal Nanostructures Probed by a Superconducting Nanowire Single-Photon Detector
journal, October 2012
- Sandberg, Richard L.; Padilha, Lazaro A.; Qazilbash, Muhammad M.
- ACS Nano, Vol. 6, Issue 11
Communication: Biexciton generation rates in CdSe nanorods are length independent
journal, February 2013
- Baer, Roi; Rabani, Eran
- The Journal of Chemical Physics, Vol. 138, Issue 5
Stochastic models of carrier dynamics in single-walled carbon nanotubes
journal, August 2005
- Barzykin, A. V.; Tachiya, M.
- Physical Review B, Vol. 72, Issue 7
Femtosecond Spectroscopy of Optical Excitations in Single-Walled Carbon Nanotubes: Evidence for Exciton-Exciton Annihilation
journal, April 2005
- Ma, Ying-Zhong; Valkunas, Leonas; Dexheimer, Susan L.
- Physical Review Letters, Vol. 94, Issue 15
Quantized Bimolecular Auger Recombination of Excitons in Single-Walled Carbon Nanotubes
journal, February 2006
- Huang, Libai; Krauss, Todd D.
- Physical Review Letters, Vol. 96, Issue 5
The Optical Resonances in Carbon Nanotubes Arise from Excitons
journal, May 2005
- Wang, F.
- Science, Vol. 308, Issue 5723
Effect of Aspect Ratio on Multiparticle Auger Recombination in Single-Walled Carbon Nanotubes: Time Domain Atomistic Simulation
journal, December 2017
- Pal, Sougata; Casanova, David; Prezhdo, Oleg V.
- Nano Letters, Vol. 18, Issue 1
Works referencing / citing this record:
Synergy effect of intraband transition and impact-Auger in optical hot-carrier solar cells
journal, August 2019
- Takeda, Yasuhiko
- Journal of Applied Physics, Vol. 126, Issue 7
Colloidal semiconductor nanocrystals in energy transfer reactions
journal, January 2019
- Moroz, Pavel; Royo Romero, Luis; Zamkov, Mikhail
- Chemical Communications, Vol. 55, Issue 21
Hot-electron dynamics in quantum dots manipulated by spin-exchange Auger interactions
journal, October 2019
- Singh, Rohan; Liu, Wenyong; Lim, Jaehoon
- Nature Nanotechnology, Vol. 14, Issue 11
Long-range exciton transport and slow annihilation in two-dimensional hybrid perovskites
journal, January 2020
- Deng, Shibin; Shi, Enzheng; Yuan, Long
- Nature Communications, Vol. 11, Issue 1
Biexciton Auger Recombination Differs in Hybrid and Inorganic Halide Perovskite Quantum Dots
journal, December 2017
- Eperon, Giles E.; Jedlicka, Erin; Ginger, David S.
- The Journal of Physical Chemistry Letters, Vol. 9, Issue 1