Superlattices are Greener on the Other Side: How Light Transforms Self-Assembled Mixed Halide Perovskite Nanocrystals

Brennan, Michael C.; Toso, Stefano; Pavlovetc, Ilia M.; Zhukovskyi, Maksym; Marras, Sergio; Kuno, Masaru; Manna, Liberato; Baranov, Dmitry

doi:10.1021/acsenergylett.0c00630

Title: Superlattices are Greener on the Other Side: How Light Transforms Self-Assembled Mixed Halide Perovskite Nanocrystals

Journal Article · Mon Apr 06 00:00:00 EDT 2020 · ACS Energy Letters

DOI:https://doi.org/10.1021/acsenergylett.0c00630· OSTI ID:1659522

^[1]; Toso, Stefano ^[2]; Pavlovetc, Ilia M. ^[3]; Zhukovskyi, Maksym ^[4]; Marras, Sergio ^[5];

^[6];

^[7];

^[7]

Department of Chemistry and Biochemistry, University of Notre Dame, Notre Dame, Indiana 46556, United States, International Doctoral Program in Science, Università Cattolica del Sacro Cuore, Via Musei 41, 25121 Brescia, Italy
International Doctoral Program in Science, Università Cattolica del Sacro Cuore, Via Musei 41, 25121 Brescia, Italy, Nanochemistry Department, Istituto Italiano di Tecnologia, Via Morego 30, 16163 Genova, Italy
Department of Chemistry and Biochemistry, University of Notre Dame, Notre Dame, Indiana 46556, United States
Notre Dame Integrated Imaging Facility, University of Notre Dame, Notre Dame, Indiana 46556, United States
Materials Characterization Facility, Istituto Italiano di Tecnologia, Via Morego 30, 16163 Genova, Italy
Department of Chemistry and Biochemistry, University of Notre Dame, Notre Dame, Indiana 46556, United States, Department of Physics, University of Notre Dame, Notre Dame, Indiana 46556, United States
Nanochemistry Department, Istituto Italiano di Tecnologia, Via Morego 30, 16163 Genova, Italy

Perovskite nanocrystal superlattices (NC SLs) are the nearest real-world approximations to monodisperse NC ensembles. NC SLs thus represent ideal model systems for evaluating the optical and structural stability of CsPb(I_1–xBr_x)₃ NCs at a macroscopic level. Here, photoinduced changes to CsPb(I_1–xBr_x)₃ NC SLs (0 < x < 1.0) are probed via in situ photoluminescence, X-ray diffraction, and electron microscopy. We find that prolonged (~10–20 h) ultraviolet–visible irradiation causes irreversible PL blueshifts, photobrightening, and crystal structure contractions. These changes stem from gradual photoinduced I₂ sublimation, which transforms CsPb(I_1–xBr_x)₃ into CsPbBr₃. Despite eliminating half of the initial halides from individual CsPb(I_0.53Br_0.47)₃ particles, NCs within SLs remarkably preserve their initial crystallinity, cuboidal shapes, edge lengths, and size distributions. This work illustrates compositional control toward generating precisely engineered perovskite NC SLs. It also highlights iodide photo-oxidation as a hurdle that must be overcome if mixed halide perovskite nanomaterials are to be applied beyond fundamental studies.

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Research Organization:: University of Notre Dame, IN (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES). Materials Sciences & Engineering Division; European Union’s Horizon 2020

Grant/Contract Number:: FC02-04ER15533; SC0014334; 794560

OSTI ID:: 1659522

Alternate ID(s):: OSTI ID: 1657793

Journal Information:: ACS Energy Letters, Journal Name: ACS Energy Letters Vol. 5 Journal Issue: 5; ISSN 2380-8195

Publisher:: American Chemical Society (ACS)Copyright Statement

Country of Publication:: United States

Language:: English

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Cited by: 41 works

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References (61)

Wide-Angle X-ray Diffraction Evidence of Structural Coherence in CsPbBr ₃ Nanocrystal Superlattices Toso, Stefano; Baranov, Dmitry; Giannini, Cinzia ACS Materials Letters, Vol. 1, Issue 2 https://doi.org/10.1021/acsmaterialslett.9b00217	journal	July 2019
Photobrightening in Lead Halide Perovskites: Observations, Mechanisms, and Future Potential Andaji‐Garmaroudi, Zahra; Anaya, Miguel; Pearson, Andrew J. Advanced Energy Materials, Vol. 10, Issue 13 https://doi.org/10.1002/aenm.201903109	journal	April 2020
Temperature-dependent photoluminescence of inorganic perovskite nanocrystal films Li, Jiaming; Yuan, Xi; Jing, Pengtao RSC Advances, Vol. 6, Issue 82 https://doi.org/10.1039/C6RA17008K	journal	January 2016
Air-Stable Surface-Passivated Perovskite Quantum Dots for Ultra-Robust, Single- and Two-Photon-Induced Amplified Spontaneous Emission Pan, Jun; Sarmah, Smritakshi P.; Murali, Banavoth The Journal of Physical Chemistry Letters, Vol. 6, Issue 24 https://doi.org/10.1021/acs.jpclett.5b02460	journal	December 2015
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
Size-Dependent Lattice Structure and Confinement Properties in CsPbI ₃ Perovskite Nanocrystals: Negative Surface Energy for Stabilization Zhao, Qian; Hazarika, Abhijit; Schelhas, Laura T. ACS Energy Letters, Vol. 5, Issue 1 https://doi.org/10.1021/acsenergylett.9b02395	journal	November 2019
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
Highly Luminescent Phase-Stable CsPbI ₃ Perovskite Quantum Dots Achieving Near 100% Absolute Photoluminescence Quantum Yield Liu, Feng; Zhang, Yaohong; Ding, Chao ACS Nano, Vol. 11, Issue 10 https://doi.org/10.1021/acsnano.7b05442	journal	September 2017
Reversible photo-induced trap formation in mixed-halide hybrid perovskites for photovoltaics Hoke, Eric T.; Slotcavage, Daniel J.; Dohner, Emma R. Chemical Science, Vol. 6, Issue 1 https://doi.org/10.1039/C4SC03141E	journal	January 2015
Metal Halide Perovskite Polycrystalline Films Exhibiting Properties of Single Crystals Brenes, Roberto; Guo, Dengyang; Osherov, Anna Joule, Vol. 1, Issue 1 https://doi.org/10.1016/j.joule.2017.08.006	journal	September 2017
The Impact of Atmosphere on the Local Luminescence Properties of Metal Halide Perovskite Grains Brenes, Roberto; Eames, Christopher; Bulović, Vladimir Advanced Materials, Vol. 30, Issue 15 https://doi.org/10.1002/adma.201706208	journal	March 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
Benzoyl Halides as Alternative Precursors for the Colloidal Synthesis of Lead-Based Halide Perovskite Nanocrystals Imran, Muhammad; Caligiuri, Vincenzo; Wang, Mengjiao Journal of the American Chemical Society, Vol. 140, Issue 7 https://doi.org/10.1021/jacs.7b13477	journal	January 2018
Thermal degradation of luminescence in inorganic perovskite CsPbBr ₃ nanocrystals Yuan, Xi; Hou, Xuemin; Li, Ji Physical Chemistry Chemical Physics, Vol. 19, Issue 13 https://doi.org/10.1039/C6CP08824D	journal	January 2017
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
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
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
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
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
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
Spontaneous Self-Assembly of Perovskite Nanocrystals into Electronically Coupled Supercrystals: Toward Filling the Green Gap Tong, Yu; Yao, En-Ping; Manzi, Aurora Advanced Materials, Vol. 30, Issue 29 https://doi.org/10.1002/adma.201801117	journal	June 2018
Structural Phase Transitions in CsPbBr ₃ Hirotsu, Shunsuke; Harada, Jimpei; Iizumi, Masashi Journal of the Physical Society of Japan, Vol. 37, Issue 5 https://doi.org/10.1143/JPSJ.37.1393	journal	November 1974
Accumulation of Deep Traps at Grain Boundaries in Halide Perovskites Park, Ji-Sang; Calbo, Joaquín; Jung, Young-Kwang ACS Energy Letters, Vol. 4, Issue 6 https://doi.org/10.1021/acsenergylett.9b00840	journal	May 2019
Controllable Self-Induced Passivation of Hybrid Lead Iodide Perovskites toward High Performance Solar Cells Chen, Qi; Zhou, Huanping; Song, Tze-Bin Nano Letters, Vol. 14, Issue 7 https://doi.org/10.1021/nl501838y	journal	June 2014
N -Bromosuccinimide as Bromide Precursor for Direct Synthesis of Stable and Highly Luminescent Green-Emitting Perovskite Nanocrystals Paul, Sumanta; Samanta, Anunay ACS Energy Letters, Vol. 5, Issue 1 https://doi.org/10.1021/acsenergylett.9b02363	journal	November 2019
Time and intensity dependence of the photolysis of lead halides Verwey, J. F. Journal of Physics and Chemistry of Solids, Vol. 31, Issue 1 https://doi.org/10.1016/0022-3697(70)90297-0	journal	January 1970
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
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
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
Precise Control of Quantum Confinement in Cesium Lead Halide Perovskite Quantum Dots via Thermodynamic Equilibrium Dong, Yitong; Qiao, Tian; Kim, Doyun Nano Letters, Vol. 18, Issue 6 https://doi.org/10.1021/acs.nanolett.8b00861	journal	May 2018
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
Controlling the Phase Segregation in Mixed Halide Perovskites through Nanocrystal Size Gualdrón-Reyes, Andrés. F.; Yoon, Seog Joon; Barea, Eva M. ACS Energy Letters, Vol. 4, Issue 1 https://doi.org/10.1021/acsenergylett.8b02207	journal	November 2018
Lead Halide Perovskite Nanocrystals: From Discovery to Self-assembly and Applications Kovalenko, Maksym V.; Bodnarchuk, Maryna I. CHIMIA International Journal for Chemistry, Vol. 71, Issue 7 https://doi.org/10.2533/chimia.2017.461	journal	August 2017
Controlling competing photochemical reactions stabilizes perovskite solar cells Motti, Silvia G.; Meggiolaro, Daniele; Barker, Alex J. Nature Photonics, Vol. 13, Issue 8 https://doi.org/10.1038/s41566-019-0435-1	journal	May 2019
To Exchange or Not to Exchange . Suppressing Anion Exchange in Cesium Lead Halide Perovskites with PbSO ₄ –Oleate Capping Ravi, Vikash Kumar; Scheidt, Rebecca A.; Nag, Angshuman ACS Energy Letters, Vol. 3, Issue 4 https://doi.org/10.1021/acsenergylett.8b00380	journal	March 2018
Scalable photonic sources using two-dimensional lead halide perovskite superlattices Jagielski, Jakub; Solari, Simon F.; Jordan, Lucie Nature Communications, Vol. 11, Issue 1 https://doi.org/10.1038/s41467-019-14084-3	journal	January 2020
Phase segregation due to ion migration in all-inorganic mixed-halide perovskite nanocrystals Zhang, Huichao; Fu, Xu; Tang, Ying Nature Communications, Vol. 10, Issue 1 https://doi.org/10.1038/s41467-019-09047-7	journal	March 2019
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
Tunable Anisotropic Photon Emission from Self-Organized CsPbBr ₃ Perovskite Nanocrystals Jurow, Matthew J.; Lampe, Thomas; Penzo, Erika Nano Letters, Vol. 17, Issue 7 https://doi.org/10.1021/acs.nanolett.7b02147	journal	June 2017
Zero-Dimensional Cesium Lead Halides: History, Properties, and Challenges Akkerman, Quinten A.; Abdelhady, Ahmed L.; Manna, Liberato The Journal of Physical Chemistry Letters, Vol. 9, Issue 9 https://doi.org/10.1021/acs.jpclett.8b00572	journal	April 2018
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
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
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
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
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
Electrochemical Hole Injection Selectively Expels Iodide from Mixed Halide Perovskite Films Samu, Gergely F.; Balog, Ádám; De Angelis, Filippo Journal of the American Chemical Society, Vol. 141, Issue 27 https://doi.org/10.1021/jacs.9b04568	journal	June 2019
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
Low-threshold amplified spontaneous emission and lasing from colloidal nanocrystals of caesium lead halide perovskites Yakunin, Sergii; Protesescu, Loredana; Krieg, Franziska Nature Communications, Vol. 6, Issue 1 https://doi.org/10.1038/ncomms9056	journal	August 2015
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
Using photoluminescence to monitor the optoelectronic properties of methylammonium lead halide perovskites in light and dark over periods of days Kheraj, Vipul; Simonds, Brian J.; Toshniwal, Aditi Journal of Luminescence, Vol. 194 https://doi.org/10.1016/j.jlumin.2017.10.021	journal	February 2018
Cooperative excitonic quantum ensemble in perovskite-assembly superlattice microcavities Zhou, Chun; Zhong, Yichi; Dong, Hongxing Nature Communications, Vol. 11, Issue 1 https://doi.org/10.1038/s41467-019-14078-1	journal	January 2020
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
Nanocube Superlattices of Cesium Lead Bromide Perovskites and Pressure-Induced Phase Transformations at Atomic and Mesoscale Levels Nagaoka, Yasutaka; Hills-Kimball, Katie; Tan, Rui Advanced Materials, Vol. 29, Issue 18 https://doi.org/10.1002/adma.201606666	journal	March 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
Thermal Stability of the Black Perovskite Phase in Cesium Lead Iodide Nanocrystals Under Humid Conditions Thomas, Cherrelle J.; Zhang, Yangning; Guillaussier, Adrien Chemistry of Materials, Vol. 31, Issue 23 https://doi.org/10.1021/acs.chemmater.9b03533	journal	November 2019
Near-Unity Photoluminescence Quantum Yield in CsPbBr ₃ Nanocrystal Solid-State Films via Postsynthesis Treatment with Lead Bromide Di Stasio, Francesco; Christodoulou, Sotirios; Huo, Nengjie Chemistry of Materials, Vol. 29, Issue 18 https://doi.org/10.1021/acs.chemmater.7b02834	journal	September 2017
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
Investigation into the Photoluminescence Red Shift in Cesium Lead Bromide Nanocrystal Superlattices Baranov, Dmitry; Toso, Stefano; Imran, Muhammad The Journal of Physical Chemistry Letters, Vol. 10, Issue 3 https://doi.org/10.1021/acs.jpclett.9b00178	journal	January 2019
The kinetics of the photolysis of thin films of lead iodide Albrecht, M. G.; Green, Mino Journal of Physics and Chemistry of Solids, Vol. 38, Issue 3 https://doi.org/10.1016/0022-3697(77)90106-8	journal	January 1977
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
Superfluorescence from lead halide perovskite quantum dot superlattices Rainò, Gabriele; Becker, Michael A.; Bodnarchuk, Maryna I. Nature, Vol. 563, Issue 7733 https://doi.org/10.1038/s41586-018-0683-0	journal	November 2018

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