A major efficiency limit for solution-processed perovskite optoelectronic devices, for example light-emitting diodes, is trap-mediated non-radiative losses. Defect passivation using organic molecules has been identified as an attractive approach to tackle this issue. However, implementation of this approach has been hindered by a lack of deep understanding of how the molecular structures influence the effectiveness of passivation. We show that the so far largely ignored hydrogen bonds play a critical role in affecting the passivation. By weakening the hydrogen bonding between the passivating functional moieties and the organic cation featuring in the perovskite, we significantly enhance the interaction with defect sites and minimize non-radiative recombination losses. Consequently, we achieve exceptionally high-performance near-infrared perovskite light-emitting diodes with a record external quantum efficiency of 21.6%. In addition, our passivated perovskite light-emitting diodes maintain a high external quantum efficiency of 20.1% and a wall-plug efficiency of 11.0% at a high current density of 200 mA cm−2, making them more attractive than the most efficient organic and quantum-dot light-emitting diodes at high excitations.
Subscribe to Journal
Get full journal access for 1 year
only $14.08 per issue
All prices are NET prices.
VAT will be added later in the checkout.
Rent or Buy article
Get time limited or full article access on ReadCube.
All prices are NET prices.
The data that support the plots within this paper and other findings of this study are available from the corresponding authors upon reasonable request.
Tan, Z.-K. et al. Bright light-emitting diodes based on organometal halide perovskite. Nat. Nanotechnol. 9, 687–692 (2014).
Akkerman, Q. A. et al. Strongly emissive perovskite nanocrystal inks for high-voltage solar cells. Nat. Energy 2, 16194 (2017).
Dou, L. et al. Solution-processed hybrid perovskite photodetectors with high detectivity. Nat. Commun. 5, 5404 (2014).
Shi, X. et al. Optical energy losses in organic–inorganic hybrid perovskite light-emitting diodes. Adv. Opt. Mater. 6, 1800667 (2018).
Stranks, S. D. & Snaith, H. J. Metal-halide perovskites for photovoltaic and light-emitting devices. Nat. Nanotechnol. 10, 391–402 (2015).
Xing, G. et al. Transcending the slow bimolecular recombination in lead-halide perovskites for electroluminescence. Nat. Commun. 8, 14558 (2017).
Li, G. et al. Efficient light-emitting diodes based on nanocrystalline perovskite in a dielectric polymer matrix. Nano Lett. 15, 2640–2644 (2015).
Xiao, Z. et al. Efficient perovskite light-emitting diodes featuring nanometre-sized crystallites. Nat. Photon. 11, 108–115 (2017).
Wang, N. et al. Perovskite light-emitting diodes based on solution-processed self-organized multiple quantum wells. Nat. Photon. 10, 699–704 (2016).
Zou, W. et al. Minimising efficiency roll-off in high-brightness perovskite light-emitting diodes. Nat. Commun. 9, 608 (2018).
Li, G. et al. Surface ligand engineering for near-unity quantum yield inorganic halide perovskite QDs and high-performance QLEDs. Chem. Mater. 30, 6099–6107 (2018).
Abdi-Jalebi, M. et al. Maximizing and stabilizing luminescence from halide perovskites with potassium passivation. Nature 555, 497–501 (2018).
Stranks, S. D. Nonradiative losses in metal halide perovskites. ACS Energy Lett. 2, 1515–1525 (2017).
Tress, W. Perovskite solar cells on the way to their radiative efficiency limit—insights into a success story of high open-circuit voltage and low recombination. Adv. Energy Mater. 7, 1602358 (2017).
Correa-Baena, J.-P. et al. Promises and challenges of perovskite solar cells. Science 358, 739–744 (2017).
Braly, I. L. et al. Hybrid perovskite films approaching the radiative limit with over 90% photoluminescence quantum efficiency. Nat. Photon. 12, 355–361 (2018).
Agiorgousis, M. L., Sun, Y. Y., Zeng, H. & Zhang, S. Strong covalency-induced recombination centers in perovskite solar cell material CH3NH3PbI3. J. Am. Chem. Soc. 136, 14570–14575 (2014).
Noel, N. K. et al. Enhanced photoluminescence and solar cell performance via Lewis base passivation of organic–inorganic lead halide perovskites. ACS Nano 8, 9815–9821 (2014).
Dequilettes, D. W. et al. Photoluminescence lifetimes exceeding 8 μs and quantum yields exceeding 30% in hybrid perovskite thin films by ligand passivation. ACS Energy Lett. 1, 438–444 (2016).
Wang, F. et al. Phenylalkylamine passivation of organolead halide perovskites enabling high-efficiency and air-stable photovoltaic cells. Adv. Mater. 28, 9986–9992 (2016).
Zheng, X. et al. Defect passivation in hybrid perovskite solar cells using quaternary ammonium halide anions and cations. Nat. Energy 2, 17102 (2017).
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).
Ma, F. et al. Stable α/δ phase junction of formamidinium lead iodide perovskites for enhanced near-infrared emission. Chem. Sci. 8, 800–805 (2016).
Cortecchia, D. et al. Broadband emission in two-dimensional hybrid perovskites: the role of structural deformation. J. Am. Chem. Soc. 139, 39–42 (2017).
Chen, Z. et al. High-performance color-tunable perovskite light emitting devices through structural modulation from bulk to layered film. Adv. Mater. 29, 1603157 (2017).
Neutzner, S., Srimath Kandada, A. R., Lanzani, G. & Petrozza, A. A dual-phase architecture for efficient amplified spontaneous emission in lead iodide perovskites. J. Mater. Chem. C 4, 4630–4633 (2016).
Yuan, M. et al. Perovskite energy funnels for efficient light-emitting diodes. Nat. Nanotechnol. 11, 872–877 (2016).
Duan, H. S. et al. The identification and characterization of defect states in hybrid organic–inorganic perovskite photovoltaics. Phys. Chem. Chem. Phys. 17, 112–116 (2015).
Bi, C. et al. Non-wetting surface-driven high-aspect-ratio crystalline grain growth for efficient hybrid perovskite solar cells. Nat. Commun. 6, 7747 (2015).
Dai, H. et al. A temperature-responsive copolymer hydrogel in controlled drug delivery. Macromolecules 39, 6584–6589 (2006).
Chen, H. et al. A solvent-and vacuum-free route to large-area perovskite films for efficient solar modules. Nature 550, 92–95 (2017).
Taylor, V. C. A. et al. Investigating the role of the organic cation in formamidinium lead iodide perovskite using ultrafast spectroscopy. J. Phys. Chem. Lett. 9, 895–901 (2018).
Gero, A. Inductive effect and hydrogen bonding as factors in the base strength of polymethylenediamines. J. Am. Chem. Soc. 76, 5159–5160 (1954).
Dai, X. et al. Solution-processed, high-performance light-emitting diodes based on quantum dots. Nature 515, 96–99 (2014).
Ly, K. T. et al. Near-infrared organic light-emitting diodes with very high external quantum efficiency and radiance. Nat. Photon. 11, 63–68 (2016).
Cao, Y. et al. Perovskite light-emitting diodes based on spontaneously formed submicrometre-scale structures. Nature 562, 249–253 (2018).
Lin, K. et al. Perovskite light-emitting diodes with external quantum efficiency exceeding 20 per cent. Nature 562, 245–248 (2018).
Xiao, X. et al. Suppressed ion migration along the in-plane. ACS Energy Lett. 3, 684–688 (2018).
Bai, S. et al. High-performance planar heterojunction perovskite solar cells: preserving long charge carrier diffusion lengths and interfacial engineering. Nano Res. 7, 1749–1758 (2014).
Perdew, J. P., Burke, K. & Ernzerhof, M. Generalized gradient approximation made simple. Phys. Rev. Lett. 77, 3865–3868 (1996).
Goedecker, S. & Teter, M. Separable dual-space Gaussian pseudopotentials. Phys. Rev. B 54, 1703–1710 (1996).
VandeVondele, J. & Hutter, J. Gaussian basis sets for accurate calculations on molecular systems in gas and condensed phases. J. Chem. Phys. 127, 114105 (2007).
De Mello, J. C., Wittmann, H. F. & Friend, R. H. An improved experimental determination of external photoluminescence quantum efficiency. Adv. Mater. 9, 230–232 (1997).
We thank O. Inganäs, T.C. Sum, S.S. Lim, J. Zhang, W. Tress, W. Chen, Y. Puttisong, Y.T. Gong, C.Y. Kuang and C. Deibel for useful discussions. This work is supported by the ERC Starting Grant (717026), the National Basic Research Program of China (973 Program, grant number 2015CB932200), the National Natural Science Foundation of China (61704077, 51572016, 51721001, 61634001, 61725502, 91733302 and U1530401), the Joint Research Program between China and the European Union (2016YFE0112000), the Natural Science Foundation of Jiangsu Province (BK20171007), the National Key Research and Development Program of China (grant number 2016YFB0700700), the European Commission Marie Skłodowska-Curie Actions (691210), the Swiss National Science Foundation (CR23I2-162828), Nanyang Technological University start-up grant M4081924, and the Swedish Government Strategic Research Area in Materials Science on Functional Materials at Linköping University (Faculty Grant SFO-Mat-LiU no. 2009-00971). The TEM measurements were performed at the Facility for Analysis, Characterization, Testing and Simulation (FACTS) in Nanyang Technological University, Singapore. A.P. and T.B. acknowledge financial support from the ERC Consolidator grant SOPHY (grant agreement number 771528). A.P. and A.J.B. acknowledge the project PERSEO-‘Perovskite-based solar cells: towards high efficiency and long-term stability’ (Bando PRIN 2015-Italian Ministry of University and Scientific Research (MIUR) Decreto Direttoriale 4 novembre 2015 n. 2488, project number 20155LECAJ) for funding. W.X. is a Wenner-Gren Postdoc Fellow; F.G. is a Wallenberg Academy Fellow.
F.G. and W.X. have filed a patent application related to this work (application no. SE1950272-3).
Publisher’s note: Springer Nature remains neutral with regard to jurisdictional claims in published maps and institutional affiliations.
About this article
Cite this article
Xu, W., Hu, Q., Bai, S. et al. Rational molecular passivation for high-performance perovskite light-emitting diodes. Nat. Photonics 13, 418–424 (2019). https://doi.org/10.1038/s41566-019-0390-x
Journal of Energy Chemistry (2021)
Materials Research Bulletin (2021)
Nano Energy (2021)
Boosting the efficiency of quasi-2D perovskites light-emitting diodes by using encapsulation growth method
Nano Energy (2021)
Boosting Efficiency and Curtailing the Efficiency Roll-Off in Green Perovskite Light-Emitting Diodes via Incorporating Ytterbium as Cathode Interface Layer
ACS Applied Materials & Interfaces (2020)