Abstract
Perovskite quantum dots (QDs) are promising for various photonic applications due to their high colour purity, tunable optoelectronic properties and excellent solution processability. Surface features impact their optoelectronic properties, and surface defects remain a major obstacle to progress. Here we develop a strategy utilizing diisooctylphosphinic acid-mediated synthesis combined with hydriodic acid-etching-driven nanosurface reconstruction to stabilize CsPbI3 QDs. Diisooctylphosphinic acid strongly adsorbs to the QDs and increases the formation energy of halide vacancies, enabling nanosurface reconstruction. The QD film with nanosurface reconstruction shows enhanced phase stability, improved photoluminescence endurance under thermal stress and electric field conditions, and a higher activation energy for ion migration. Consequently, we demonstrate perovskite light-emitting diodes (LEDs) that feature an electroluminescence peak at 644 nm. These LEDs achieve an external quantum efficiency of 28.5% and an operational half-lifetime surpassing 30 h at an initial luminance of 100 cd m−2, marking a tenfold improvement over previously published studies. The integration of these high-performance LEDs with specifically designed thin-film transistor circuits enables the demonstration of solution-processed active-matrix perovskite displays that show a peak external quantum efficiency of 23.6% at a display brightness of 300 cd m−2. This work showcases nanosurface reconstruction as a pivotal pathway towards high-performance QD-based optoelectronic devices.
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The data that support the findings of this study are available from the corresponding authors upon reasonable request. Source data are provided with this paper.
References
Liu, X. K. et al. Metal halide perovskites for light-emitting diodes. Nat. Mater. 20, 10–21 (2021).
Dey, A. et al. State of the art and prospects for halide perovskite nanocrystals. ACS Nano 15, 10775–10981 (2021).
Hassan, Y. et al. Ligand-engineered bandgap stability in mixed-halide perovskite LEDs. Nature 591, 72–77 (2021).
Jiang, Y. et al. Synthesis-on-substrate of quantum dot solids. Nature 612, 679–684 (2022).
Kim, J. S. et al. Ultra-bright, efficient and stable perovskite light-emitting diodes. Nature 611, 688–694 (2022).
Wang, Y. et al. All-inorganic quantum-dot LEDs based on a phase-stabilized α-CsPbI3 perovskite. Angew. Chem. Int. Ed. 60, 16164–16170 (2021).
Mir, W. J. et al. Lecithin capping ligands enable ultrastable perovskite-phase CsPbI3 quantum dots for Rec. 2020 bright-red light-emitting diodes. J. Am. Chem. Soc. 144, 13302–13310 (2022).
Boles, M. A., Ling, D., Hyeon, T. & Talapin, D. V. The surface science of nanocrystals. Nat. Mater. 15, 141–153 (2016).
Chiba, T. et al. Anion-exchange red perovskite quantum dots with ammonium iodine salts for highly efficient light-emitting devices. Nat. Photonics 12, 681–687 (2018).
Yang, J.-N. et al. Potassium bromide surface passivation on CsPbI3−xBrx nanocrystals for efficient and stable pure red perovskite light-emitting diodes. J. Am. Chem. Soc. 142, 2956–2967 (2020).
Shen, X. et al. Bright and efficient pure red perovskite nanocrystals light‐emitting devices via in situ modification. Adv. Funct. Mater. 32, 2110048 (2022).
Zhang, J. et al. A multifunctional “halide-equivalent” anion enabling efficient CsPb(Br/I)3 nanocrystals pure-red light-emitting diodes with external quantum efficiency exceeding 23. Adv. Mater. 35, 2209002 (2023).
Zhang, J. et al. Ligand-induced cation–π interactions enable high-efficiency, bright, and spectrally stable Rec. 2020 pure-red perovskite light-emitting diodes. Adv. Mater. 35, 2303938 (2023).
Vashishtha, P. & Halpert, J. E. Field-driven ion migration and color instability in red-emitting mixed halide perovskite nanocrystal light-emitting diodes. Chem. Mater. 29, 5965–5973 (2017).
Barker, A. J. et al. Defect-assisted photoinduced halide segregation in mixed-halide perovskite thin films. ACS Energy Lett. 2, 1416–1424 (2017).
Xie, M. et al. High-efficiency pure-red perovskite quantum-dot light-emitting diodes. Nano Lett. 22, 8266–8273 (2022).
Lan, Y. et al. Spectrally stable and efficient pure red CsPbI3 quantum dot light-emitting diodes enabled by sequential ligand post-treatment strategy. Nano Lett. 21, 8756–8763 (2021).
Zhou, Y. et al. Perovskite anion exchange: a microdynamics model and a polar adsorption strategy for precise control of luminescence color. Adv. Funct. Mater. 31, 2106871 (2021).
Chen, D. et al. Amino acid-passivated pure red CsPbI3 quantum dot LEDs. ACS Energy Lett. 8, 410–416 (2022).
Song, Y.-H. et al. Planar defect-free pure red perovskite light-emitting diodes via metastable phase crystallization. Sci. Adv. 8, eabq2321 (2022).
De Roo, J. et al. Highly dynamic ligand binding and light absorption coefficient of cesium lead bromide perovskite nanocrystals. ACS Nano 10, 2071–2081 (2016).
Fiuza-Maneiro, N. et al. Ligand chemistry of inorganic lead halide perovskite nanocrystals. ACS Energy Lett. 8, 1152–1191 (2023).
Yuan, M. et al. Perovskite energy funnels for efficient light-emitting diodes. Nat. Nanotechnol. 11, 872–877 (2016).
Xu, L. et al. A bilateral interfacial passivation strategy promoting efficiency and stability of perovskite quantum dot light-emitting diodes. Nat. Commun. 11, 3902 (2020).
Zhu, R., Luo, Z., Chen, H., Dong, Y. & Wu, S.-T. Realizing Rec. 2020 color gamut with quantum dot displays. Opt. Express 23, 23680–23693 (2015).
Han, T.-H. et al. A roadmap for the commercialization of perovskite light emitters. Nat. Rev. Mater. 7, 757–777 (2022).
Protesescu, L. et al. Nanocrystals of cesium lead halide perovskites (CsPbX3, X = Cl, Br, and I): novel optoelectronic materials showing bright emission with wide color gamut. Nano Lett. 15, 3692–3696 (2015).
Zhang, Q. et al. α-BaF2 nanoparticle substrate-enabled γ-CsPbI3 heteroepitaxial growth for efficient and bright deep-red light-emitting diodes. J. Am. Chem. Soc. 144, 8162–8170 (2022).
Das, S. & Samanta, A. Highly luminescent and phase-stable red/NIR-emitting all-inorganic and hybrid perovskite nanocrystals. ACS Energy Lett. 6, 3780–3787 (2021).
Zhong, Q. et al. L-type ligand-assisted acid-free synthesis of CsPbBr3 nanocrystals with near-unity photoluminescence quantum yield and high stability. Nano Lett. 19, 4151–4157 (2019).
Woo, J. Y. et al. Highly stable cesium lead halide perovskite nanocrystals through in situ lead halide inorganic passivation. Chem. Mater. 29, 7088–7092 (2017).
Yang, D. et al. Surface halogen compensation for robust performance enhancements of CsPbX3 perovskite quantum dots. Adv. Opt. Mater. 7, 1900276 (2019).
Almeida, G. et al. Role of acid–base equilibria in the size, shape, and phase control of cesium lead bromide nanocrystals. ACS Nano 12, 1704–1711 (2018).
Zhang, B. et al. Alkyl phosphonic acids deliver CsPbBr3 nanocrystals with high photoluminescence quantum yield and truncated octahedron shape. Chem. Mater. 31, 9140–9147 (2019).
Li, Y. et al. Highly luminescent and stable CsPbBr3 perovskite quantum dots modified by phosphine ligands. Nano Res. 12, 785–789 (2019).
Motti, S. G. et al. Controlling competing photochemical reactions stabilizes perovskite solar cells. Nat. Photonics 13, 532–539 (2019).
Meggiolaro, D., Mosconi, E. & De Angelis, F. Formation of surface defects dominates ion migration in lead-halide perovskites. ACS Energy Lett. 4, 779–785 (2019).
Udayabhaskararao, T. et al. A mechanistic study of phase transformation in perovskite nanocrystals driven by ligand passivation. Chem. Mater. 30, 84–93 (2018).
Yarita, N. et al. Dynamics of charged excitons and biexcitons in CsPbBr3 perovskite nanocrystals revealed by femtosecond transient-absorption and single-dot luminescence spectroscopy. J. Phys. Chem. Lett. 8, 1413–1418 (2017).
Li, C. et al. Insights into ultrafast carrier dynamics in perovskite thin films and solar cells. ACS Photonics 7, 1893–1907 (2020).
Huang, J., Yuan, Y., Shao, Y. & Yan, Y. Understanding the physical properties of hybrid perovskites for photovoltaic applications. Nat. Rev. Mater. 2, 17042 (2017).
Shen, X. et al. Zn-alloyed CsPbI3 nanocrystals for highly efficient perovskite light-emitting devices. Nano Lett. 19, 1552–1559 (2019).
Sutton, R. J. et al. Cubic or orthorhombic? Revealing the crystal structure of metastable black-phase CsPbI3 by theory and experiment. ACS Energy Lett. 3, 1787–1794 (2018).
Zou, W. et al. Minimising efficiency roll-off in high-brightness perovskite light-emitting diodes. Nat. Commun. 9, 608 (2018).
Lin, X. et al. Electrically-driven single-photon sources based on colloidal quantum dots with near-optimal antibunching at room temperature. Nat. Commun. 8, 1132 (2017).
Yuan, Y. & Huang, J. Ion migration in organometal trihalide perovskite and its impact on photovoltaic efficiency and stability. Acc. Chem. Res. 49, 286–293 (2016).
Li, D. et al. Electronic and ionic transport dynamics in organolead halide perovskites. ACS Nano 10, 6933–6941 (2016).
Zhang, B.-B. et al. Defect proliferation in CsPbBr3 crystal induced by ion migration. Appl. Phys. Lett. 116, 063505 (2020).
Li, H. et al. In-situ reacted multiple-anchoring ligands to produce highly photo-thermal resistant CsPbI3 quantum dots for display backlights. Chem. Eng. J. 454, 140038 (2023).
Dong, Y. et al. Precise control of quantum confinement in cesium lead halide perovskite quantum dots via thermodynamic equilibrium. Nano Lett. 18, 3716–3722 (2018).
Dai, X. et al. Solution-processed, high-performance light-emitting diodes based on quantum dots. Nature 515, 96–99 (2014).
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).
Zhang, Z. et al. High-performance, solution-processed, and insulating-layer-free light-emitting diodes based on colloidal quantum dots. Adv. Mater. 30, 1801387 (2018).
Liu, Y. et al. Efficient blue light-emitting diodes based on quantum-confined bromide perovskite nanostructures. Nat. Photonics 13, 760–764 (2019).
Blöchl, P. E. Projector augmented-wave method. Phys. Rev. B 50, 17953–17979 (1994).
Kresse, G. & Furthmüller, J. Efficient iterative schemes for ab initio total-energy calculations using a plane-wave basis set. Phys. Rev. B 54, 11169–11186 (1996).
Kresse, G. & Furthmüller, J. Efficiency of ab-initio total energy calculations for metals and semiconductors using a plane-wave basis set. Comput. Mater. Sci. 6, 15–50 (1996).
Grimme, S., Antony, J., Ehrlich, S. & Krieg, H. A consistent and accurate ab initio parametrization of density functional dispersion correction (DFT-D) for the 94 elements H–Pu. J. Chem. Phys. 132, 154104 (2010).
Grimme, S., Ehrlich, S. & Goerigk, L. Effect of the damping function in dispersion corrected density functional theory. J. Comput. Chem. 32, 1456–1465 (2011).
Acknowledgements
This work was financially supported by the National Natural Science Foundation of China (52102188, X.D.; 52172159, J.H.), the Key Research and Development Program of Zhejiang Province (2021C01030, Z.Y.), the Natural Science Foundation of Zhejiang Province (LQ21F040005, X.D.), the Young Elite Scientists Sponsorship Program by CAST (YESS20210444, X.D.), the science and technology projects of the Institute of Wenzhou, Zhejiang University (XMGL-KJZX-202302, X.D.), the Fundamental Research Funds for the Central Universities (17241022301, X.D.) and the Shanxi-Zheda Institute of Advanced Materials and Chemical Engineering (2022SZ-TD004, H.H.). X.D. gratefully acknowledges the support of the Zhejiang University Education Foundation Qizhen Scholar Foundation. H.L. sincerely thanks J. Huang for his support. We thank J. Li and Y. He for their assistance in the synthesis of the QDs and device fabrication.
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X.D. and H.L. conceived the idea and designed the experiments. X.D., J.H. and Z.Y. supervised the work. H.L. carried out the synthesis of nanocrystals, device fabrication and characterizations. Y.F. and Y.G. assisted in characterizations. M.Z., Q. Cui and Q. Cai participated in optical measurements. K.Y. and C.F. conducted the theoretical calculation. J.H. and H.H. provided helpful suggestions. X.D. and H.L. wrote the first draught of the manuscript. J.H. and Z.Y. provided major revisions. All authors discussed the results and commented on the manuscript.
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Extended data
Extended Data Fig. 1 Absorption and UPS spectra.
a, The plots of (αhν)2 versus the photon energy calculated from the absorption measurement. b, UPS spectra of the OA-QDs, DSPA-QDs, and NR-QDs: Photoemission cutoff region (left) and the valence-band-edge region (right). EVB and ECB are calculated with the formula: EVB = Ecutoff + ΔE; ECB = EVB – Eoptical bandgap. c, UPS spectra of PTAA/TAPC and PEDOT:PSS:PFI, showing photoemission cutoff region (up) and the valence-band-edge region (down).
Extended Data Fig. 2 Nanosurface reconstruction of the blue-emitting CsPbBr3 QDs.
a–c, Absorption spectra (a), PL spectra (b), and time-resolved PL decay curves (c) of the purified CsPbBr3 QDs in solution. d–f, TEM images of the OA-BQDs (d), DSPA-BQDs (e), and NR-BQDs (f), respectively. The scale bar is 50 nm. Insets show the corresponding size distribution histograms of the QDs. g, The time-dependent PL intensity trajectory of the QD films at 100 oC. h, Typical current density–voltage–luminance (J-V-L) and i, EQE–luminance (EQE-L) characteristics of the PeLEDs based on OA-BQDs, DSPA-BQDs, and NR-BQDs, respectively. The results show successful nanosurface reconstruction of the ultrasmall CsPbBr3 QDs with the improved optoelectronic properties utilizing the diisooctylphosphinic acid-mediated synthesis combined with hydrobromic acid etching.
Extended Data Fig. 3 Performance of PeLEDs based on multi-layer NR-QD films.
a, J-V-L, b, EQE–L characteristics, and c, T50 for the PeLEDs with emitter thicknesses of 5-7 nm (monolayer), 10-12 nm, 16-18 nm, and 22-25 nm, respectively. The device performance decreases following the increase of thickness of QDs emissive layers.
Extended Data Fig. 4 In-situ PL monitoring during the synthesis process.
a, Schematic diagram of the in-situ PL monitoring setup, in which 365 nm ultraviolet light is irradiated onto the sample, and the fluorescence signal is collected using a fiber-coupled spectrometer after the injection of cesium precursor. b, c Colour map of spectral evolution of the DSPA-QDs (b) and OA-QDs (c), where the arrows indicate the moment of HI injection. The DSPA-QDs show an obvious spectra blue shift after HI injection while the OA-QDs show no spectra change. Note: The in-situ measured PL spectrum shows a slight redshift compared with the PL spectrum collected in dilute QDs solution, which is caused by the reabsorption effects of the crude QDs solution with a high concentration.
Extended Data Fig. 5 XPS analysis.
High-resolution XPS spectra of (a) Pb 4 f, (b) I 3d, and (c) Cs 1 s of the DSPA-QDs, NR-QDs (TMPI), and NR-QDs (TBAI: tetrabutylammonium iodide). For the NR-QDs, the results show a slight shift of Pb 4f towards high binding energy. The core-level spectra of I 3d and Cs 1 s remain nearly identical. Surface Pb in the DSPA-QDs is nonideally coordinated compared with the NR-QDs. The iodine is bonded with Pb and oleylammonium (NH3+) in both QDs. TMPI (phosphinium iodine) was added into the purified NR-QD solution to further passivate the surface halide vacancy. We replaced TMPI with TBAI and did not observe the difference in additional bonding or electrical interaction in core-level spectra of I 3d and Cs 1s. The result suggests that a slight amount of phosphinium does not influence the chemical circumstance of iodine in the NR-QDs.
Extended Data Fig. 6 Transient absorption measurements.
Full-timescale transient absorption plots in a pseudo-colour 2D representation of the (a) OA-QDs, (b) DSPA-QDs, and (c) NR-QDs, respectively. d–f, The femtosecond transient absorption spectra of the (d) OA-QDs, (e) DSPA-QDs, and (f) NR-QDs at different delay times.
Extended Data Fig. 7 Characteristics of PeLEDs under consecutive scans.
a, J-V-L, b, EQE–L characteristics for the OA-QD-based LEDs. c, J-V-L, d, EQE–L characteristics for the DSPA-QD-based LEDs. e, J-V-L, f, EQE–L characteristics for the NR-QD-based LEDs. The peak EQEs decrease following the consecutive scans.
Extended Data Fig. 8 Ion migration activation energy measurement.
a–c, The time-dependent currents from 248 K to 298 K by applying bias at 30 V for the (a) NR-QD film, (b) DSPA-QD film, and (c) OA-QD film, respectively. d–f, The fitting data from the current decay plots of the (d) NR-QD film, (e) DSPA-QD film, and (f) OA-QD film. The τ1 is independent of temperature, which relates to the equipment response. The τ2 represents the time constant of ion migration and is used for calculating the activation energy.
Extended Data Fig. 9 Performance of the active matrix PeLED based on NR-QDs.
a, Box plot of the peak CE and peak EQE of different pixels. n = 7 independent replicates. The box plots display the median and interquartile range, with the upper whiskers extending to largest value ≤ 1.5 × interquartile range from the 75th percentile and the lower whiskers extending to the smallest values ≤ 1.5 × interquartile range from the 25th percentile. b, Operational stability of eight active matrix PeLEDs measured at all-on state, showing a half lifetime around 12-22 h.
Supplementary information
Supplementary Information
Supplementary Figs. 1–18 and Tables 1–5.
Supplementary Video 1
HI injection into the OA reaction system.
Supplementary Video 2
HI injection into the DSPA reaction system.
Supplementary Video 3
Independently controllable emission of active-matrix displays.
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Li, H., Feng, Y., Zhu, M. et al. Nanosurface-reconstructed perovskite for highly efficient and stable active-matrix light-emitting diode display. Nat. Nanotechnol. (2024). https://doi.org/10.1038/s41565-024-01652-y
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DOI: https://doi.org/10.1038/s41565-024-01652-y