Supramolecular assembly of blue and green halide perovskites with near-unity photoluminescence

Zhu, Cheng; Jin, Jianbo; Wang, Zhen; Xu, Zhenpeng; Folgueras, Maria C.; Jiang, Yuxin; Uzundal, Can B.; Le, Han D.; Wang, Feng; Zheng, Xiaoyu (Rayne); Yang, Peidong

doi:10.1126/science.adi4196

Title: Supramolecular assembly of blue and green halide perovskites with near-unity photoluminescence

Journal Article · 04 January 2024 · Science

DOI: https://doi.org/10.1126/science.adi4196 · OSTI ID:2329272

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Univ. of California, Berkeley, CA (United States); Lawrence Berkeley National Laboratory (LBNL), Berkeley, CA (United States); Kavli Energy NanoScience Institute, Berkeley, CA (United States)
Univ. of California, Berkeley, CA (United States)
Lawrence Berkeley National Laboratory (LBNL), Berkeley, CA (United States); Univ. of California, Berkeley, CA (United States)
Lawrence Berkeley National Laboratory (LBNL), Berkeley, CA (United States); Kavli Energy NanoScience Institute, Berkeley, CA (United States); Univ. of California, Berkeley, CA (United States)
Univ. of California, Berkeley, CA (United States); Lawrence Berkeley National Laboratory (LBNL), Berkeley, CA (United States)

The metal-halide ionic octahedron is the optoelectronic unit for halide perovskites, and a crown ether–assisted supramolecular assembly approach can pack various ionic octahedra into tunable symmetries. In this work, we demonstrate near-unity photoluminescence quantum yield (PLQY) blue and green emission with the supramolecular assembly of hafnium (Hf) and zirconium (Zr) halide octahedral clusters. (18C6@K)₂HfBr₆ powders showed blue emission with a near-unity PLQY (96.2%), and green emission was also achieved with (18C6@K)₂ZrCl₄Br₂ powders at a PLQY of 82.7%. In conclusion, these highly emissive powders feature facile low-temperature solution-based synthesis conditions and maintain high PLQY in solution-processable semiconductor inks under ambient conditions, and they were used in thin-film displays and emissive three-dimensional–printed architectures that exhibited high spatial resolution.

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Research Organization:: Lawrence Berkeley National Laboratory (LBNL), Berkeley, CA (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES). Materials Sciences & Engineering Division (MSE)

Grant/Contract Number:: AC02-05CH11231

OSTI ID:: 2329272

Journal Information:: Science, Journal Name: Science Journal Issue: 6678 Vol. 383; ISSN 0036-8075

Publisher:: AAASCopyright Statement

Country of Publication:: United States

Language:: English

References (66)

Lead‐Free Perovskite Variant Solid Solutions Cs ₂ Sn _1– _x Te _x Cl ₆ : Bright Luminescence and High Anti‐Water Stability Tan, Zhifang; Chu, Yanmeng; Chen, Jinxi Advanced Materials, Vol. 32, Issue 32 https://doi.org/10.1002/adma.202002443	journal	June 2020
Lead‐Free Perovskite Derivative Cs ₂ SnCl ₆₋ _x Br _x Single Crystals for Narrowband Photodetectors Zhou, Jun; Luo, Jiajun; Rong, Ximing Advanced Optical Materials, Vol. 7, Issue 10 https://doi.org/10.1002/adom.201900139	journal	March 2019
Bis-Tridentate Iridium(III) Phosphors with Very High Photostability and Fabrication of Blue-Emitting OLEDs Kuo, Hsin-Hung; Zhu, Ze-lin; Lee, Chun-Sing Advanced Science, Vol. 5, Issue 9 https://doi.org/10.1002/advs.201800846	journal	July 2018
Bandgap-Tunable Cesium Lead Halide Perovskites with High Thermal Stability for Efficient Solar Cells Sutton, Rebecca J.; Eperon, Giles E.; Miranda, Laura Advanced Energy Materials, Vol. 6, Issue 8 https://doi.org/10.1002/aenm.201502458	journal	February 2016
Controlling Photoluminescence and Photocatalysis Activities in Lead‐Free Cs ₂ Pt _x Sn _{1− x} Cl ₆ Perovskites via Ion Substitution Yin, Hang; Chen, Junsheng; Guan, Peng Angewandte Chemie International Edition, Vol. 60, Issue 42 https://doi.org/10.1002/anie.202108133	journal	September 2021
Materials Design and Discovery with High-Throughput Density Functional Theory: The Open Quantum Materials Database (OQMD) Saal, James E.; Kirklin, Scott; Aykol, Muratahan JOM, Vol. 65, Issue 11 https://doi.org/10.1007/s11837-013-0755-4	journal	September 2013
Darstellung von HfCl4 und HfBr4 durch umsetzung von hafnium mit geschmolzenen metallhalogeniden Thomas, W.; Elias, H. Journal of Inorganic and Nuclear Chemistry, Vol. 38, Issue 12 https://doi.org/10.1016/0022-1902(76)80199-6	journal	January 1976
Synthesis of gallium nitride by ammonia injection into gallium melt Shibata, M.; Furuya, T.; Sakaguchi, H. Journal of Crystal Growth, Vol. 196, Issue 1 https://doi.org/10.1016/S0022-0248(98)00819-7	journal	January 1999
Ionic liquid assisted pure blue emission CsPbBr3 quantum dots with improved optical properties and alkyl chain regulated stability Luo, Hao; Huang, Yuqiong; Liu, Hongli Chemical Engineering Journal, Vol. 430 https://doi.org/10.1016/j.cej.2021.132790	journal	February 2022
Fabrication and materials properties of polystyrene/carbon nanotube (PS/CNT) composites: A review Kaseem, Mosab; Hamad, Kotiba; Ko, Young Gun European Polymer Journal, Vol. 79 https://doi.org/10.1016/j.eurpolymj.2016.04.011	journal	June 2016
Crystal growth and scintillation properties of Thallium-based halide scintillators van Loef, Edgar V.; Ciampi, Guido; Shirwadkar, Urmila Journal of Crystal Growth, Vol. 532 https://doi.org/10.1016/j.jcrysgro.2019.125438	journal	February 2020
Cs2HfCl6 doped with Zr: Influence of tetravalent substitution on scintillation properties Vaněček, V.; Páterek, J.; Král, R. Journal of Crystal Growth, Vol. 573 https://doi.org/10.1016/j.jcrysgro.2021.126307	journal	November 2021
The making of a reconfigurable semiconductor with a soft ionic lattice Gao, Mengyu; Zhang, Ye; Lin, Zhenni Matter, Vol. 4, Issue 12 https://doi.org/10.1016/j.matt.2021.09.023	journal	December 2021
Single-crystal growth, structure and luminescence properties of Cs2HfCl3Br3 Kodama, Shohei; Kurosawa, Shunsuke; Fujii, Kotaro Optical Materials, Vol. 106 https://doi.org/10.1016/j.optmat.2020.109942	journal	August 2020
First-principles study on structural stability and reaction with H2O and O2 of vacancy-ordered double perovskite halides: Cs2(Ti, Zr, Hf)X6 Kaewmeechai, Chaiyawat; Laosiritaworn, Yongyut; Jaroenjittichai, Atchara Punya Results in Physics, Vol. 25 https://doi.org/10.1016/j.rinp.2021.104225	journal	June 2021
Making and Breaking of Lead Halide Perovskites Manser, Joseph S.; Saidaminov, Makhsud I.; Christians, Jeffrey A. Accounts of Chemical Research, Vol. 49, Issue 2 https://doi.org/10.1021/acs.accounts.5b00455	journal	January 2016
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
Lattice Dynamics and Optoelectronic Properties of Vacancy-Ordered Double Perovskite Cs₂TeX₆ (X = Cl^–, Br^–, I^–) Single Crystals Folgueras, Maria C.; Jin, Jianbo; Gao, Mengyu The Journal of Physical Chemistry C, Vol. 125, Issue 45 https://doi.org/10.1021/acs.jpcc.1c08332	journal	November 2021
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
Bright Tail States in Blue-Emitting Ultrasmall Perovskite Quantum Dots Li, Jing; Gan, Lu; Fang, Zhishan The Journal of Physical Chemistry Letters, Vol. 8, Issue 24 https://doi.org/10.1021/acs.jpclett.7b02786	journal	December 2017
A New Perspective and Design Principle for Halide Perovskites: Ionic Octahedron Network (ION) Jin, Jianbo; Folgueras, Maria C.; Gao, Mengyu Nano Letters, Vol. 21, Issue 12 https://doi.org/10.1021/acs.nanolett.1c01897	journal	June 2021
Ligand-Free Processable Perovskite Semiconductor Ink Folgueras, Maria C.; Louisia, Sheena; Jin, Jianbo Nano Letters, Vol. 21, Issue 20 https://doi.org/10.1021/acs.nanolett.1c03308	journal	October 2021
Highly Deformable High-Performance Paper-Based Perovskite Photodetector with Improved Stability Li, Shun-Xin; Xu, Xiao-Lu; Yang, Ying ACS Applied Materials & Interfaces, Vol. 13, Issue 27 https://doi.org/10.1021/acsami.1c05828	journal	July 2021
Defect Tolerance in Methylammonium Lead Triiodide Perovskite Steirer, K. Xerxes; Schulz, Philip; Teeter, Glenn ACS Energy Letters, Vol. 1, Issue 2 https://doi.org/10.1021/acsenergylett.6b00196	journal	July 2016
Original Core–Shell Structure of Cubic CsPbBr ₃ @Amorphous CsPbBr _x Perovskite Quantum Dots with a High Blue Photoluminescence Quantum Yield of over 80% Wang, Shixun; Bi, Chenghao; Yuan, Jifeng ACS Energy Letters, Vol. 3, Issue 1 https://doi.org/10.1021/acsenergylett.7b01243	journal	November 2017
Tellurium-Based Double Perovskites A₂TeX₆ with Tunable Band Gap and Long Carrier Diffusion Length for Optoelectronic Applications Ju, Dianxing; Zheng, Xiaopeng; Yin, Jun ACS Energy Letters, Vol. 4, Issue 1 https://doi.org/10.1021/acsenergylett.8b02113	journal	December 2018
Highly Stable Organic Antimony Halide Crystals for X-ray Scintillation He, Qingquan; Zhou, Chenkun; Xu, Liangjin ACS Materials Letters, Vol. 2, Issue 6 https://doi.org/10.1021/acsmaterialslett.0c00133	journal	May 2020
Colloidal Synthesis and Optical Properties of Perovskite-Inspired Cesium Zirconium Halide Nanocrystals Abfalterer, Anna; Shamsi, Javad; Kubicki, Dominik J. ACS Materials Letters, Vol. 2, Issue 12 https://doi.org/10.1021/acsmaterialslett.0c00393	journal	November 2020
Giant Electron–Phonon Coupling and Deep Conduction Band Resonance in Metal Halide Double Perovskite Steele, Julian A.; Puech, Pascal; Keshavarz, Masoumeh ACS Nano, Vol. 12, Issue 8 https://doi.org/10.1021/acsnano.8b02936	journal	July 2018
Supramolecular Assembly of Halide Perovskite Building Blocks Zhu, Cheng; Jin, Jianbo; Gao, Mengyu Journal of the American Chemical Society, Vol. 144, Issue 27 https://doi.org/10.1021/jacs.2c04357	journal	June 2022
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
High Photoluminescence Efficiency and Optically Pumped Lasing in Solution-Processed Mixed Halide Perovskite Semiconductors Deschler, Felix; Price, Michael; Pathak, Sandeep The Journal of Physical Chemistry Letters, Vol. 5, Issue 8 https://doi.org/10.1021/jz5005285	journal	March 2014
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
Steric engineering of metal-halide perovskites with tunable optical band gaps Filip, Marina R.; Eperon, Giles E.; Snaith, Henry J. Nature Communications, Vol. 5, Issue 1 https://doi.org/10.1038/ncomms6757	journal	December 2014
The Open Quantum Materials Database (OQMD): assessing the accuracy of DFT formation energies Kirklin, Scott; Saal, James E.; Meredig, Bryce npj Computational Materials, Vol. 1, Issue 1 https://doi.org/10.1038/npjcompumats.2015.10	journal	December 2015
Electron–phonon interaction in efficient perovskite blue emitters Gong, Xiwen; Voznyy, Oleksandr; Jain, Ankit Nature Materials, Vol. 17, Issue 6 https://doi.org/10.1038/s41563-018-0081-x	journal	May 2018
Charge-programmed three-dimensional printing for multi-material electronic devices Hensleigh, Ryan; Cui, Huachen; Xu, Zhenpeng Nature Electronics, Vol. 3, Issue 4 https://doi.org/10.1038/s41928-020-0391-2	journal	April 2020
Multipass inkjet printed planar methylammonium lead iodide perovskite solar cells Mathies, Florian; Abzieher, Tobias; Hochstuhl, Adam Journal of Materials Chemistry A, Vol. 4, Issue 48 https://doi.org/10.1039/C6TA07972E	journal	January 2016
Luminescent zero-dimensional organic metal halide hybrids with near-unity quantum efficiency Zhou, Chenkun; Lin, Haoran; Tian, Yu Chemical Science, Vol. 9, Issue 3 https://doi.org/10.1039/C7SC04539E	journal	January 2018
Blue-emitting bis-tridentate Ir( iii ) phosphors: OLED performances vs. substituent effects Kuo, Hsin-Hung; Hsu, Ling-Yang; Tso, Jen-Yung Journal of Materials Chemistry C, Vol. 6, Issue 39 https://doi.org/10.1039/C8TC03194K	journal	January 2018
Revealing the nature of photoluminescence emission in the metal-halide double perovskite Cs 2 AgBiBr 6 Zelewski, S. J.; Urban, J. M.; Surrente, A. Journal of Materials Chemistry C, Vol. 7, Issue 27 https://doi.org/10.1039/C9TC02402F	journal	January 2019
Recent progress of zero-dimensional luminescent metal halides Li, Mingze; Xia, Zhiguo Chemical Society Reviews, Vol. 50, Issue 4 https://doi.org/10.1039/D0CS00779J	journal	January 2021
Impact of noncovalent interactions on structural and photophysical properties of zero-dimensional tellurium(iv) perovskites Nicholas, Aaron D.; Walusiak, Benjamin W.; Garman, Leah C. Journal of Materials Chemistry C, Vol. 9, Issue 9 https://doi.org/10.1039/D0TC06000C	journal	January 2021
Transparent and flexible thin films of ZnO-polystyrene nanocomposite for UV-shielding applications Tu, Yao; Zhou, Li; Jin, Yi Zheng Journal of Materials Chemistry, Vol. 20, Issue 8 https://doi.org/10.1039/b914156a	journal	January 2010
Luminescence of Pt4+ in Octahedral Complexes Douglas, I. N.; Nicholas, J. V.; Wybourne, B. G. The Journal of Chemical Physics, Vol. 48, Issue 3 https://doi.org/10.1063/1.1668827	journal	February 1968
Determination of the absolute internal quantum efficiency of photoluminescence in GaN co-doped with Si and Zn Reshchikov, M. A.; Foussekis, M.; McNamara, J. D. Journal of Applied Physics, Vol. 111, Issue 7 https://doi.org/10.1063/1.3699312	journal	April 2012
Unusual defect physics in CH ₃ NH ₃ PbI ₃ perovskite solar cell absorber Yin, Wan-Jian; Shi, Tingting; Yan, Yanfa Applied Physics Letters, Vol. 104, Issue 6 https://doi.org/10.1063/1.4864778	journal	February 2014
Temperature-dependent photoluminescence of cesium lead halide perovskite (CsPbX ₃ , X = Br, Cl, I) quantum dots Song, Yuchen; Zhang, Xiaosong; Li, Lan Materials Research Express, Vol. 6, Issue 11 https://doi.org/10.1088/2053-1591/ab4911	journal	September 2019
Self-Consistent Equations Including Exchange and Correlation Effects Kohn, W.; Sham, L. J. Physical Review, Vol. 140, Issue 4A, p. A1133-A1138 https://doi.org/10.1103/PhysRev.140.A1133	journal	November 1965
Optical investigations of defects in Cd 1 − x Zn x Te Stadler, W.; Hofmann, D. M.; Alt, H. C. Physical Review B, Vol. 51, Issue 16 https://doi.org/10.1103/PhysRevB.51.10619	journal	April 1995
Binding energy for the intrinsic excitons in wurtzite GaN Shan, W.; Little, B. D.; Fischer, A. J. Physical Review B, Vol. 54, Issue 23 https://doi.org/10.1103/PhysRevB.54.16369	journal	December 1996
Exciton-phonon interactions, exciton binding energy, and their importance in the realization of room-temperature semiconductor lasers based on GaN Viswanath, Annamraju Kasi; Lee, Joo In; Kim, Dongho Physical Review B, Vol. 58, Issue 24 https://doi.org/10.1103/PhysRevB.58.16333	journal	December 1998
Analysis of the temperature and excitation intensity dependencies of photoluminescence in undoped GaN films Reshchikov, M. A.; Korotkov, R. Y. Physical Review B, Vol. 64, Issue 11 https://doi.org/10.1103/PhysRevB.64.115205	journal	August 2001
Origin of the nonradiative decay of bound excitons in GaN nanowires Hauswald, Christian; Corfdir, Pierre; Zettler, Johannes K. Physical Review B, Vol. 90, Issue 16 https://doi.org/10.1103/PhysRevB.90.165304	journal	October 2014
Norm-Conserving Pseudopotentials Hamann, D. R.; Schlüter, M.; Chiang, C. Physical Review Letters, Vol. 43, Issue 20 https://doi.org/10.1103/PhysRevLett.43.1494	journal	November 1979
OLEX2 : a complete structure solution, refinement and analysis program Dolomanov, Oleg V.; Bourhis, Luc J.; Gildea, Richard J. Journal of Applied Crystallography, Vol. 42, Issue 2 https://doi.org/10.1107/S0021889808042726	journal	January 2009
Formability of ABX ₃ ( X = F, Cl, Br, I) halide perovskites Li, Chonghea; Lu, Xionggang; Ding, Weizhong Acta Crystallographica Section B Structural Science, Vol. 64, Issue 6 https://doi.org/10.1107/S0108768108032734	journal	November 2008
Crystal structure refinement with SHELXL Sheldrick, George M. Acta Crystallographica Section C Structural Chemistry, Vol. 71, Issue 1, p. 3-8 https://doi.org/10.1107/S2053229614024218	journal	January 2015
SHELXT – Integrated space-group and crystal-structure determination Sheldrick, George M. Acta Crystallographica Section A Foundations and Advances, Vol. 71, Issue 1, p. 3-8 https://doi.org/10.1107/S2053273314026370	journal	January 2015
Stabilizing black-phase formamidinium perovskite formation at room temperature and high humidity Hui, Wei; Chao, Lingfeng; Lu, Hui Science, Vol. 371, Issue 6536 https://doi.org/10.1126/science.abf7652	journal	March 2021
Design and printing of proprioceptive three-dimensional architected robotic metamaterials Cui, Huachen; Yao, Desheng; Hensleigh, Ryan Science, Vol. 376, Issue 6599 https://doi.org/10.1126/science.abn0090	journal	June 2022
Further Contribution to the Theory of the Line-Shape of the Exciton Absorption Band Toyozawa, Yutaka Progress of Theoretical Physics, Vol. 27, Issue 1 https://doi.org/10.1143/PTP.27.89	journal	January 1962
First principles methods using CASTEP Clark, Stewart J.; Segall, Matthew D.; Pickard, Chris J. Zeitschrift für Kristallographie - Crystalline Materials, Vol. 220, Issue 5/6 https://doi.org/10.1524/zkri.220.5.567.65075	journal	January 2005
Studies on the photodegradation of red, green and blue phosphorescent OLED emitters Schmidbauer, Susanna; Hohenleutner, Andreas; König, Burkhard Beilstein Journal of Organic Chemistry, Vol. 9 https://doi.org/10.3762/bjoc.9.245	journal	January 2013
Comparative study of scintillation properties of Cs ₂ HfCl ₆ and Cs ₂ ZrCl ₆ Saeki, Keiichiro; Fujimoto, Yutaka; Koshimizu, Masanori Applied Physics Express, Vol. 9, Issue 4 https://doi.org/10.7567/APEX.9.042602	journal	March 2016
Luminescence and scintillation properties of Cs₂HfBr₆ and Cs₂ZrBr₆ crystals Saeki, Keiichiro; Fujimoto, Yutaka; Koshimizu, Masanori Japanese Journal of Applied Physics, Vol. 57, Issue 3 https://doi.org/10.7567/JJAP.57.030310	journal	February 2018

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