Universal Size-Dependent Stokes Shifts in Lead Halide Perovskite Nanocrystals

Brennan, Michael C.; Forde, Aaron; Zhukovskyi, Maksym; Baublis, Andrew J.; Morozov, Yurii V.; Zhang, Shubin; Zhang, Zhuoming; Kilin, Dmitri S.; Kuno, Masaru

doi:10.1021/acs.jpclett.0c01407

Title: Universal Size-Dependent Stokes Shifts in Lead Halide Perovskite Nanocrystals

Journal Article · Mon Jun 01 00:00:00 EDT 2020 · Journal of Physical Chemistry Letters

DOI:https://doi.org/10.1021/acs.jpclett.0c01407· OSTI ID:1657792

^[1]; Forde, Aaron ^[2]; Zhukovskyi, Maksym ^[3]; Baublis, Andrew J. ^[4]; Morozov, Yurii V. ^[4]; Zhang, Shubin ^[4]; Zhang, Zhuoming ^[4];

^[2];

^[4]

Univ. of Notre Dame, IN (United States); Univ. Cattolica del Sacro Cuore, Brescia (Italy)
North Dakota State Univ., Fargo, ND (United States)
Notre Dame Integrated Imaging Facility, Notre Dame, Indiana 46556, United States
Univ. of Notre Dame, IN (United States)

Size-dependent photoluminescence Stokes shifts (ΔE_s) universally exist in CsPbX₃ (X = Cl^–, Br^–, or I^–) perovskite nanocrystals (NCs). ΔE_s values, which range from ~15 to 100 meV for NCs with average edge lengths (l) from approximately 13 to 3 nm, are halide-dependent such that ΔE_s(CsPbI₃) > ΔE_s(CsPbBr₃) ≳ ΔE_s(CsPbCl₃). Observed size-dependent Stokes shifts are not artifacts of ensemble size distributions as demonstrated through measurements of single CsPbBr₃ NC Stokes shifts ((ΔE_s) = 42 ± 5 meV), which are in near quantitative agreement with associated ensemble (l = 6.8 ± 0.8 nm) ΔE_s values (ΔE_s ≈ 50 meV). Transient differential absorption measurements additionally illustrate no significant spectral dynamics on the picosecond time scale that would contribute to ΔE_s. This excludes polaron formation as being responsible for ΔE_s. Overall, the results point to an origin for ΔE_s, intrinsic to the size-dependent electronic properties of individual perovskite NCs.

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Research Organization:: Univ. of Notre Dame, IN (United States); Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States). National Energy Research Scientific Computing Center (NERSC)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES). Materials Sciences & Engineering Division; US Air Force Office of Scientific Research (AFOSR); National Science Foundation (NSF)

Grant/Contract Number:: SC0014334; FC02-04ER15533; 91202; AC02-05CH11231; CHE-2004197

OSTI ID:: 1657792

Journal Information:: Journal of Physical Chemistry Letters, Vol. 11, Issue 13; ISSN 1948-7185

Publisher:: American Chemical SocietyCopyright Statement

Country of Publication:: United States

Language:: English

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Cited by: 29 works

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References (53)

Nanocrystals of Cesium Lead Halide Perovskites (CsPbX ₃ , X = Cl, Br, and I): Novel Optoelectronic Materials Showing Bright Emission with Wide Color Gamut Protesescu, Loredana; Yakunin, Sergii; Bodnarchuk, Maryna I. Nano Letters, Vol. 15, Issue 6 https://doi.org/10.1021/nl5048779	journal	February 2015
Properties and potential optoelectronic applications of lead halide perovskite nanocrystals Kovalenko, Maksym V.; Protesescu, Loredana; Bodnarchuk, Maryna I. Science, Vol. 358, Issue 6364 https://doi.org/10.1126/science.aam7093	journal	November 2017
Genesis, challenges and opportunities for colloidal lead halide perovskite nanocrystals Akkerman, Quinten A.; Rainò, Gabriele; Kovalenko, Maksym V. Nature Materials, Vol. 17, Issue 5 https://doi.org/10.1038/s41563-018-0018-4	journal	February 2018
Lead Halide Perovskite Nanocrystals in the Research Spotlight: Stability and Defect Tolerance Huang, He; Bodnarchuk, Maryna I.; Kershaw, Stephen V. ACS Energy Letters, Vol. 2, Issue 9 https://doi.org/10.1021/acsenergylett.7b00547	journal	August 2017
Quantum dot-induced phase stabilization of -CsPbI3 perovskite for high-efficiency photovoltaics Swarnkar, A.; Marshall, A. R.; Sanehira, E. M. Science, Vol. 354, Issue 6308 https://doi.org/10.1126/science.aag2700	journal	October 2016
Enhanced mobility CsPbI ₃ quantum dot arrays for record-efficiency, high-voltage photovoltaic cells Sanehira, Erin M.; Marshall, Ashley R.; Christians, Jeffrey A. Science Advances, Vol. 3, Issue 10 https://doi.org/10.1126/sciadv.aao4204	journal	October 2017
Rationalizing the light-induced phase separation of mixed halide organic–inorganic perovskites Draguta, Sergiu; Sharia, Onise; Yoon, Seog Joon Nature Communications, Vol. 8, Issue 1 https://doi.org/10.1038/s41467-017-00284-2	journal	August 2017
Vacancy-Mediated Anion Photosegregation Kinetics in Mixed Halide Hybrid Perovskites: Coupled Kinetic Monte Carlo and Optical Measurements Ruth, Anthony; Brennan, Michael C.; Draguta, Sergiu ACS Energy Letters, Vol. 3, Issue 10 https://doi.org/10.1021/acsenergylett.8b01369	journal	September 2018
Photoluminescence Up-Conversion in CsPbBr ₃ Nanocrystals Morozov, Yurii V.; Zhang, Shubin; Brennan, Michael C. ACS Energy Letters, Vol. 2, Issue 10 https://doi.org/10.1021/acsenergylett.7b00902	journal	October 2017
Progress in laser cooling semiconductor nanocrystals and nanostructures Zhang, Shubin; Zhukovskyi, Maksym; Jankó, Boldizsár NPG Asia Materials, Vol. 11, Issue 1 https://doi.org/10.1038/s41427-019-0156-4	journal	October 2019
High Defect Tolerance in Lead Halide Perovskite CsPbBr ₃ Kang, Jun; Wang, Lin-Wang The Journal of Physical Chemistry Letters, Vol. 8, Issue 2 https://doi.org/10.1021/acs.jpclett.6b02800	journal	January 2017
Surface Termination, Morphology, and Bright Photoluminescence of Cesium Lead Halide Perovskite Nanocrystals ten Brinck, Stephanie; Infante, Ivan ACS Energy Letters, Vol. 1, Issue 6 https://doi.org/10.1021/acsenergylett.6b00595	journal	November 2016
Role of Acid–Base Equilibria in the Size, Shape, and Phase Control of Cesium Lead Bromide Nanocrystals Almeida, Guilherme; Goldoni, Luca; Akkerman, Quinten ACS Nano, Vol. 12, Issue 2 https://doi.org/10.1021/acsnano.7b08357	journal	January 2018
Essentially Trap-Free CsPbBr ₃ Colloidal Nanocrystals by Postsynthetic Thiocyanate Surface Treatment Koscher, Brent A.; Swabeck, Joseph K.; Bronstein, Noah D. Journal of the American Chemical Society, Vol. 139, Issue 19 https://doi.org/10.1021/jacs.7b02817	journal	May 2017
Shape-Pure, Nearly Monodispersed CsPbBr ₃ Nanocubes Prepared Using Secondary Aliphatic Amines Imran, Muhammad; Ijaz, Palvasha; Baranov, Dmitry Nano Letters, Vol. 18, Issue 12 https://doi.org/10.1021/acs.nanolett.8b03598	journal	November 2018
Design Principles for Trap-Free CsPbX ₃ Nanocrystals: Enumerating and Eliminating Surface Halide Vacancies with Softer Lewis Bases Nenon, David P.; Pressler, Kimo; Kang, Jun Journal of the American Chemical Society, Vol. 140, Issue 50 https://doi.org/10.1021/jacs.8b11035	journal	November 2018
The Underlying Chemical Mechanism of Selective Chemical Etching in CsPbBr ₃ Nanocrystals for Reliably Accessing Near-Unity Emitters Koscher, Brent A.; Nett, Zachary; Alivisatos, A. Paul ACS Nano, Vol. 13, Issue 10 https://doi.org/10.1021/acsnano.9b05782	journal	September 2019
Bidentate Ligand-Passivated CsPbI ₃ Perovskite Nanocrystals for Stable Near-Unity Photoluminescence Quantum Yield and Efficient Red Light-Emitting Diodes Pan, Jun; Shang, Yuequn; Yin, Jun Journal of the American Chemical Society, Vol. 140, Issue 2 https://doi.org/10.1021/jacs.7b10647	journal	December 2017
Crystal Structure of Individual CsPbBr ₃ Perovskite Nanocubes Brennan, Michael C.; Kuno, Masaru; Rouvimov, Sergei Inorganic Chemistry, Vol. 58, Issue 2 https://doi.org/10.1021/acs.inorgchem.8b03078	journal	December 2018
On the crystal structure of colloidally prepared CsPbBr ₃ quantum dots Cottingham, Patrick; Brutchey, Richard L. Chemical Communications, Vol. 52, Issue 30 https://doi.org/10.1039/C6CC01088A	journal	January 2016
Depressed Phase Transitions and Thermally Persistent Local Distortions in CsPbBr ₃ Quantum Dots Cottingham, Patrick; Brutchey, Richard L. Chemistry of Materials, Vol. 30, Issue 19 https://doi.org/10.1021/acs.chemmater.8b02295	journal	September 2018
Coherent Nanotwins and Dynamic Disorder in Cesium Lead Halide Perovskite Nanocrystals Bertolotti, Federica; Protesescu, Loredana; Kovalenko, Maksym V. ACS Nano, Vol. 11, Issue 4 https://doi.org/10.1021/acsnano.7b00017	journal	April 2017
Existence of a Size-Dependent Stokes Shift in CsPbBr ₃ Perovskite Nanocrystals Brennan, Michael C.; Zinna, Jessica; Kuno, Masaru ACS Energy Letters, Vol. 2, Issue 7 https://doi.org/10.1021/acsenergylett.7b00383	journal	June 2017
Superlattices are Greener on the Other Side: How Light Transforms Self-Assembled Mixed Halide Perovskite Nanocrystals Brennan, Michael C.; Toso, Stefano; Pavlovetc, Ilia M. ACS Energy Letters, Vol. 5, Issue 5 https://doi.org/10.1021/acsenergylett.0c00630	journal	April 2020
Origin of the Size-Dependent Stokes Shift in CsPbBr ₃ Perovskite Nanocrystals Brennan, Michael C.; Herr, John E.; Nguyen-Beck, Triet S. Journal of the American Chemical Society, Vol. 139, Issue 35 https://doi.org/10.1021/jacs.7b05683	journal	August 2017
Excited-State Dynamics of a CsPbBr ₃ Nanocrystal Terminated with Binary Ligands: Sparse Density of States with Giant Spin–Orbit Coupling Suppresses Carrier Cooling Forde, Aaron; Inerbaev, Talgat; Hobbie, Erik K. Journal of the American Chemical Society, Vol. 141, Issue 10 https://doi.org/10.1021/jacs.8b13385	journal	February 2019
Phonon-Mediated and Weakly Size-Dependent Electron and Hole Cooling in CsPbBr ₃ Nanocrystals Revealed by Atomistic Simulations and Ultrafast Spectroscopy Boehme, Simon C.; Brinck, Stephanie ten; Maes, Jorick Nano Letters, Vol. 20, Issue 3 https://doi.org/10.1021/acs.nanolett.9b05051	journal	February 2020
External stokes shift of perovskite nanocrystals enlarged by photon recycling Gan, Zhixing; Chen, Weijian; Yuan, Lin Applied Physics Letters, Vol. 114, Issue 1 https://doi.org/10.1063/1.5081805	journal	January 2019
Origins of Stokes Shift in PbS Nanocrystals Voznyy, Oleksandr; Levina, Larissa; Fan, Fengjia Nano Letters, Vol. 17, Issue 12 https://doi.org/10.1021/acs.nanolett.7b01843	journal	November 2017
Dynamic emission Stokes shift and liquid-like dielectric solvation of band edge carriers in lead-halide perovskites Guo, Yinsheng; Yaffe, Omer; Hull, Trevor D. Nature Communications, Vol. 10, Issue 1 https://doi.org/10.1038/s41467-019-09057-5	journal	March 2019
Fast Anion-Exchange in Highly Luminescent Nanocrystals of Cesium Lead Halide Perovskites (CsPbX ₃ , X = Cl, Br, I) Nedelcu, Georgian; Protesescu, Loredana; Yakunin, Sergii Nano Letters, Vol. 15, Issue 8 https://doi.org/10.1021/acs.nanolett.5b02404	journal	July 2015
Tuning the Optical Properties of Cesium Lead Halide Perovskite Nanocrystals by Anion Exchange Reactions Akkerman, Quinten A.; D’Innocenzo, Valerio; Accornero, Sara Journal of the American Chemical Society, Vol. 137, Issue 32 https://doi.org/10.1021/jacs.5b05602	journal	August 2015
Formation of nanoscale spatially indirect excitons: Evolution of the type-II optical character of CdTe/CdSe heteronanocrystals de Mello Donegá, Celso Physical Review B, Vol. 81, Issue 16 https://doi.org/10.1103/PhysRevB.81.165303	journal	April 2010
Encapsulation of colloid perovskite nanocrystals into solid polymer matrices: Impact on electronic transition and photoluminescence Hu, Yujing; Shu, Junpeng; Zhang, Xiaowei Journal of Luminescence, Vol. 219 https://doi.org/10.1016/j.jlumin.2019.116938	journal	March 2020
Charge Carriers in Hybrid Organic–Inorganic Lead Halide Perovskites Might Be Protected as Large Polarons Zhu, X. -Y.; Podzorov, V. The Journal of Physical Chemistry Letters, Vol. 6, Issue 23 https://doi.org/10.1021/acs.jpclett.5b02462	journal	November 2015
Dynamic Disorder Dominates Delocalization, Transport, and Recombination in Halide Perovskites Munson, Kyle T.; Kennehan, Eric R.; Doucette, Grayson S. Chem, Vol. 4, Issue 12 https://doi.org/10.1016/j.chempr.2018.09.001	journal	December 2018
Suppressed phase separation of mixed-halide perovskites confined in endotaxial matrices Wang, Xi; Ling, Yichuan; Lian, Xiujun Nature Communications, Vol. 10, Issue 1 https://doi.org/10.1038/s41467-019-08610-6	journal	February 2019
Light-Induced Anion Phase Segregation in Mixed Halide Perovskites Brennan, Michael C.; Draguta, Sergiu; Kamat, Prashant V. ACS Energy Letters, Vol. 3, Issue 1 https://doi.org/10.1021/acsenergylett.7b01151	journal	November 2017
Photoinduced Anion Segregation in Mixed Halide Perovskites Brennan, Michael C.; Ruth, Anthony; Kamat, Prashant V. Trends in Chemistry, Vol. 2, Issue 4 https://doi.org/10.1016/j.trechm.2020.01.010	journal	April 2020
Fully unconstrained noncollinear magnetism within the projector augmented-wave method Hobbs, D.; Kresse, G.; Hafner, J. Physical Review B, Vol. 62, Issue 17 https://doi.org/10.1103/PhysRevB.62.11556	journal	November 2000
Calculation of the magnetic anisotropy with projected-augmented-wave methodology and the case study of disordered ${Fe}_{1 - x} {Co}_{x}$ alloys Steiner, Soner; Khmelevskyi, Sergii; Marsmann, Martijn Physical Review B, Vol. 93, Issue 22 https://doi.org/10.1103/PhysRevB.93.224425	journal	June 2016
Spinor Dynamics in Pristine and Mn ²⁺ -Doped CsPbBr ₃ NC: Role of Spin–Orbit Coupling in Ground- and Excited-State Dynamics Forde, Aaron; Inerbaev, Talgat; Kilin, Dmitri The Journal of Physical Chemistry C, Vol. 122, Issue 45 https://doi.org/10.1021/acs.jpcc.8b05392	journal	October 2018
Importance of Spin–Orbit Coupling in Hybrid Organic/Inorganic Perovskites for Photovoltaic Applications Even, Jacky; Pedesseau, Laurent; Jancu, Jean-Marc The Journal of Physical Chemistry Letters, Vol. 4, Issue 17 https://doi.org/10.1021/jz401532q	journal	August 2013
Spin–Orbit Interactions Greatly Accelerate Nonradiative Dynamics in Lead Halide Perovskites Li, Wei; Zhou, Liujiang; Prezhdo, Oleg V. ACS Energy Letters, Vol. 3, Issue 9 https://doi.org/10.1021/acsenergylett.8b01226	journal	August 2018
Band-edge exciton in quantum dots of semiconductors with a degenerate valence band: Dark and bright exciton states Efros, Al. L.; Rosen, M.; Kuno, M. Physical Review B, Vol. 54, Issue 7 https://doi.org/10.1103/PhysRevB.54.4843	journal	August 1996
The band edge luminescence of surface modified CdSe nanocrystallites: Probing the luminescing state Kuno, M.; Lee, J. K.; Dabbousi, B. O. The Journal of Chemical Physics, Vol. 106, Issue 23 https://doi.org/10.1063/1.473875	journal	June 1997
Comparative study on the excitons in lead-halide-based perovskite-type crystals CH₃NH₃PbBr₃ CH₃NH₃PbI₃ Tanaka, Kenichiro; Takahashi, Takayuki; Ban, Takuma Solid State Communications, Vol. 127, Issue 9-10, p. 619-623 https://doi.org/10.1016/S0038-1098(03)00566-0	journal	September 2003
Bright triplet excitons in caesium lead halide perovskites Becker, Michael A.; Vaxenburg, Roman; Nedelcu, Georgian Nature, Vol. 553, Issue 7687 https://doi.org/10.1038/nature25147	journal	January 2018
Exciton Fine Structure in Perovskite Nanocrystals Sercel, Peter C.; Lyons, John L.; Wickramaratne, Darshana Nano Letters, Vol. 19, Issue 6 https://doi.org/10.1021/acs.nanolett.9b01467	journal	April 2019
Composition-Dependent Energy Splitting between Bright and Dark Excitons in Lead Halide Perovskite Nanocrystals Chen, Lan; Li, Bin; Zhang, Chunfeng Nano Letters, Vol. 18, Issue 3 https://doi.org/10.1021/acs.nanolett.8b00184	journal	February 2018
The ground exciton state of formamidinium lead bromide perovskite nanocrystals is a singlet dark state Tamarat, Philippe; Bodnarchuk, Maryna I.; Trebbia, Jean-Baptiste Nature Materials, Vol. 18, Issue 7 https://doi.org/10.1038/s41563-019-0364-x	journal	May 2019
Neutral and Charged Exciton Fine Structure in Single Lead Halide Perovskite Nanocrystals Revealed by Magneto-optical Spectroscopy Fu, Ming; Tamarat, Philippe; Huang, He Nano Letters, Vol. 17, Issue 5 https://doi.org/10.1021/acs.nanolett.7b00064	journal	April 2017
Transient Energy Reservoir in 2D Perovskites Gan, Zhixing; Wen, Xiaoming; Zhou, Chunhua Advanced Optical Materials, Vol. 7, Issue 22 https://doi.org/10.1002/adom.201900971	journal	August 2019

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