Triplet management for efficient perovskite light-emitting diodes

ABSTRACT Perovskite light-emitting diodes are promising for next-generation lighting and displays because of their high colour purity and performance1. Although the management of singlet and

triplet excitons is fundamental to the design of efficient organic light-emitting diodes, the nature of how excitons affect performance is still not clear in perovskite2,3,4 and

quasi-two-dimensional (2D) perovskite-based devices5,6,7,8,9. Here, we show that triplet excitons are key to efficient emission in green quasi-2D perovskite devices and that quenching of

triplets by the organic cation is a major loss path. Employing an organic cation with a high triplet energy level (phenylethylammonium) in a quasi-2D perovskite based on formamidinium lead

bromide yields efficient harvesting of triplets. Furthermore, we show that upconversion of triplets to singlets can occur, making 100% harvesting of electrically generated excitons

potentially possible. The external quantum and current efficiencies of our green (527 nm) devices reached 12.4% and 52.1 cd A−1, respectively. Access through your institution Buy or

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DIODES Article 21 April 2022 EFFICIENT BLUE ELECTROLUMINESCENCE FROM REDUCED-DIMENSIONAL PEROVSKITES Article 26 January 2024 RECENT PROGRESS IN TRIPLET ENERGY TRANSFER SYSTEMS TOWARD ORGANIC

AFTERGLOW MATERIALS Article Open access 21 March 2025 DATA AVAILABILITY The data that support the plots within this paper and other findings of this study are available from the

corresponding author upon reasonable request. REFERENCES * Kim, Y.-H., Cho, H. & Lee, T.-W. Metal halide perovskite light emitters. _Proc. Natl Acad. Sci. USA_ 113, 11694–11702 (2016).

Article  ADS  Google Scholar  * Sutherland, B. R. & Sargent, E. H. Perovskite photonic sources. _Nat. Photon._ 10, 295–302 (2016). Article  ADS  Google Scholar  * Manser, J. S.,

Christians, J. A. & Kamat, P. V. Intriguing optoelectronic properties of metal halide perovskites. _Chem. Rev._ 116, 12956–13008 (2016). Article  Google Scholar  * Grancini, G. et al.

Role of microstructure in the electron–hole interaction of hybrid lead halide perovskites. _Nat. Photon._ 9, 695–701 (2015). Article  ADS  Google Scholar  * Tsai, H. et al. High-efficiency

two-dimensional Ruddlesden–Popper perovskite solar cells. _Nature_ 536, 312–316 (2016). Article  ADS  Google Scholar  * Chen, Y. et al. 2D Ruddlesden–Popper perovskites for optoelectronics.

_Adv. Mater._ 30, 1703487 (2018). Article  Google Scholar  * Yuan, M. et al. Perovskite energy funnels for efficient light-emitting diodes. _Nat. Nanotechnol._ 11, 872–877 (2016). Article 

ADS  Google Scholar  * Wang, N. et al. Perovskite light-emitting diodes based on solution-processed self-organized multiple quantum wells. _Nat. Photon._ 10, 699–704 (2016). Article  ADS 

Google Scholar  * Xiao, Z. et al. Efficient perovskite light-emitting diodes featuring nanometre-sized crystallites. _Nat. Photon._ 11, 108–115 (2017). Article  ADS  Google Scholar  *

Correa-Baena, J.-P. et al. The rapid evolution of highly efficient perovskite solar cells. _Energy Environ. Sci._ 10, 710–727 (2017). Article  Google Scholar  * Ummadisingu, A. et al. The

effect of illumination on the formation of metal halide perovskite films. _Nature_ 545, 208–212 (2017). Article  ADS  Google Scholar  * Matsushima, T. et al. Solution-processed

organic–inorganic perovskite field-effect transistors with high hole mobilities. _Adv. Mater._ 28, 10275–10281 (2016). Article  Google Scholar  * Cho, H. et al. Overcoming the

electroluminescence efficiency limitations of perovskite light emitting diodes. _Science_ 350, 1222–1225 (2015). Article  ADS  Google Scholar  * Yang, X. et al. Efficient green

light-emitting diodes based on quasi-two-dimensional composition and phase engineered perovskite with surface passivation. _Nat. Commun._ 9, 570 (2018). Article  ADS  Google Scholar  * Tan,

Z. K. et al. Bright light-emitting diodes based on organometal halide perovskite. _Nat. Nanotechnol._ 9, 687–692 (2014). Article  ADS  Google Scholar  * Quan, L. et al. Tailoring the energy

landscape in quasi-2D halide perovskites enables efficient green-light emission. _Nano Lett._ 17, 3701–3709 (2017). Article  ADS  Google Scholar  * Cao, Y. et al. Perovskite light-emitting

diodes based on spontaneously formed submicrometre-scale structures. _Nature_ 562, 249–253 (2018). Article  ADS  Google Scholar  * Zhao, B. et al. High-efficiency perovskite-polymer bulk

heterostructure light-emitting diodes. _Nat. Photon._ 12, 783–789 (2018). Article  ADS  Google Scholar  * Xu, W. et al. Rational molecular passivation for high-performance perovskite

light-emitting diodes. _Nat. Photon._ 13, 418–424 (2019). Article  ADS  Google Scholar  * Udagawa, K. et al. Low-driving-voltage blue phosphorescent organic light-emitting devices with

external quantum efficiency of 30%. _Adv. Mater._ 26, 5062–5066 (2014). Article  Google Scholar  * Becker, M. A. et al. Bright triplet excitons in caesium lead halide perovskites. _Nature_

553, 189–193 (2018). Article  ADS  Google Scholar  * Ema, K., Inomata, M., Kato, Y., Kunugita, H. & Era, M. Nearly perfect triplet–triplet energy transfer from Wannier excitons to

naphthalene in organic–inorganic hybrid quantum-well materials. _Phy. Rev. Lett._ 100, 257401 (2008). Article  ADS  Google Scholar  * Förster, T. Intermolecular energy migration and

fluorescence. _Ann. Phys._ 437, 55–75 (1948). Article  Google Scholar  * Dexter, D. L. A theory of sensitized luminescence in solids. _J. Chem. Phys._ 21, 836–850 (1953). Article  ADS 

Google Scholar  * Mitzi, D. B., Chondroudis, K. & Kagan, C. R. Design, structure and optical properties of organic–inorganic perovskites containing an oligothiophene chromophore. _Inorg.

Chem._ 38, 6246–6456 (1999). Article  Google Scholar  * Braun, M., Tuffentsammer, W., Wachtel, H. & Wolf, H. C. Pyrene as emitting chromophore in organic–inorganic lead halide-based

layered perovskites with different halides. _Chem. Phys. Lett._ 307, 373–378 (1999). Article  ADS  Google Scholar  * Era, M., Maeda, K. & Tsutsui, T. Enhanced phosphorescence from

naphthalene-chromophore incorporated into lead bromide-based layered perovskite having organic–inorganic superlattice structure. _Chem. Phys. Lett._ 296, 417–420 (1998). Article  ADS  Google

Scholar  * Wang, X. et al. Transient absorption probe of intermolecular triplet excimer of naphthalene in fluid solutions: identification of the species based on comparison to the

intramolecular triplet excimers of covalently-linked dimers. _J. Chem. Phys. A_ 104, 1461–1465 (2000). Article  Google Scholar  * Wu, X. et al. Trap states in lead iodide perovskites. _J.

Am. Chem. Soc._ 137, 2089–2096 (2015). Article  Google Scholar  * Younts, R. et al. Efficient generation of long-lived triplet excitons in 2D hybrid perovskite. _Adv. Mater._ 29, 1604278

(2017). Article  Google Scholar  * Chirvony, V. et al. Delayed luminescence in lead halide perovskite nanocrystals. _J. Phy. Chem. C_ 121, 13381–13390 (2017). Article  Google Scholar  *

Kitazawa, N. & Watanabe, Y. Optical properties of natural quantum-well compounds (C6H5-C_n_H2_n_-NH3)2PbBr4 (_n_ = 1–4). _J. Phys. Chem. Solids_ 71, 797–802 (2010). Article  ADS  Google

Scholar  * Saba, M. et al. Correlated electron–hole plasma in organometal perovskites. _Nat. Commun._ 5, 5049 (2014). Article  ADS  Google Scholar  * Uoyama, H., Goushi, K., Shizu, K.,

Nomura, H. & Adachi, C. Highly efficient organic light-emitting diodes from delayed fluorescence. _Nature_ 492, 234–238 (2012). Article  ADS  Google Scholar  * Qin, C., Matsushima, T.,

Fujihara, T., Potscavage, W. J. Jr & Adachi, C. Degradation mechanisms of solution-processed planar perovskite solar cells: thermally stimulated current measurement for analysis of

carrier traps. _Adv. Mater._ 28, 466–471 (2016). Article  Google Scholar  * Kaji, H. et al. Purely organic electroluminescent material realizing 100% conversion from electricity to light.

_Nat. Commun._ 6, 8476 (2015). Article  ADS  Google Scholar  * Zhang, Z. et al. The role of trap-assisted recombination in luminescent properties of organometal halide CH3NH3PbBr3 perovskite

films and quantum dots. _Sci. Rep._ 6, 27286 (2016). Article  ADS  Google Scholar  * Muniz, F. T. L., Miranda, M. A. R., Morilla dos Santos, C. & Sasaki, J. M. The Scherrer equation and

the dynamical theory of X-ray diffraction. _Acta Crystallogr. A_ 72, 385–390 (2016). Article  MathSciNet  Google Scholar  Download references ACKNOWLEDGEMENTS This work was supported by the

Japan Science and Technology Agency (JST), ERATO, Adachi Molecular Exciton Engineering Project under JST ERATO grant no. JPMJER1305, Japan, and the International Institute for Carbon

Neutral Energy Research (WPI-I2CNER) sponsored by the Ministry of Education, Culture, Sports, Science and Technology (MEXT), and The Canon Foundation. C.Q. acknowledges support from funding

by the Changchun Institute of Applied Chemistry (CIAC). We thank Pohang Accelerator Laboratory (PAL) for giving us the opportunity to perform the GIWAXS measurements and MEST and POSTECH for

supporting these experiments, H. Ahn for adjustments and help, and other colleagues from the 9A USAXS beamline for assistance. Part of this work at Kyoto was supported by JST-CREST (grant

no. JPMJCR16N3). This research was supported in part by the CNRS (PICS N8 8085), France. AUTHOR INFORMATION AUTHORS AND AFFILIATIONS * Center for Organic Photonics and Electronics Research

(OPERA), c/o Japan Science and Technology Agency (JST), ERATO, Adachi Molecular Exciton Engineering Project, Kyushu University, Fukuoka, Japan Chuanjiang Qin, Toshinori Matsushima, William

J. Potscavage Jr, Atula S. D. Sandanayaka, Matthew R. Leyden, Fatima Bencheikh, Kenichi Goushi & Chihaya Adachi * State Key Laboratory of Polymer Physics and Chemistry, Changchun

Institute of Applied Chemistry (CIAC), Chinese Academy of Sciences, Changchun, China Chuanjiang Qin * International Institute for Carbon-Neutral Energy Research (WPI-I2CNER), Kyushu

University, Fukuoka, Japan Toshinori Matsushima, Kenichi Goushi & Chihaya Adachi * Sorbonne Université, Institut Parisien de Chimie Moléculaire, UMR 8232, Chimie des Polymères, Paris,

France Fabrice Mathevet * Institut de Physique et Chimie des Matériaux de Strasbourg, UMR 7504, CNRS – Université de Strasbourg, Strasbourg, France Benoît Heinrich * Institute for Chemical

Research, Kyoto University, Kyoto, Japan Go Yumoto & Yoshihiko Kanemitsu * Innovative Organic Device Laboratory, Institute of Systems, Information Technologies and Nano-technologies

(ISIT), Fukuoka, Japan Chihaya Adachi * Fukuoka i3-Center for Organic Photonics and Electronics Research (i3-OPERA), Fukuoka, Japan Chihaya Adachi Authors * Chuanjiang Qin View author

publications You can also search for this author inPubMed Google Scholar * Toshinori Matsushima View author publications You can also search for this author inPubMed Google Scholar * William

J. Potscavage Jr View author publications You can also search for this author inPubMed Google Scholar * Atula S. D. Sandanayaka View author publications You can also search for this author

inPubMed Google Scholar * Matthew R. Leyden View author publications You can also search for this author inPubMed Google Scholar * Fatima Bencheikh View author publications You can also

search for this author inPubMed Google Scholar * Kenichi Goushi View author publications You can also search for this author inPubMed Google Scholar * Fabrice Mathevet View author

publications You can also search for this author inPubMed Google Scholar * Benoît Heinrich View author publications You can also search for this author inPubMed Google Scholar * Go Yumoto

View author publications You can also search for this author inPubMed Google Scholar * Yoshihiko Kanemitsu View author publications You can also search for this author inPubMed Google

Scholar * Chihaya Adachi View author publications You can also search for this author inPubMed Google Scholar CONTRIBUTIONS C.Q. and C.A. conceived the concept. C.Q. designed all experiments

and fabricated devices. C.Q. and T.M. performed the optical absorption, electroluminescence measurements and device characterization. F.M., B.H. and C.Q. performed GIWAX and XRD analysis.

C.Q. and K.G. measured temperature-dependent transient photoluminescence. C.Q., G.Y., K.G. and Y.K. performed transient absorption measurement and analysis. F.B. performed the simulations.

C.Q., W.J.P., M.R.L. and A.S.D.S. performed data analysis and figure preparation. C.Q. wrote the draft. All authors discussed the results and commented on the manuscript. C.A. supervised the

project. CORRESPONDING AUTHORS Correspondence to Chuanjiang Qin or Chihaya Adachi. ETHICS DECLARATIONS COMPETING INTERESTS The authors declare no competing interests. ADDITIONAL INFORMATION

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Energy transfer mechanisms, photoluminescence data and external quantum efficiency statistics. RIGHTS AND PERMISSIONS Reprints and permissions ABOUT THIS ARTICLE CITE THIS ARTICLE Qin, C.,

Matsushima, T., Potscavage, W.J. _et al._ Triplet management for efficient perovskite light-emitting diodes. _Nat. Photonics_ 14, 70–75 (2020). https://doi.org/10.1038/s41566-019-0545-9

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