Nanosurface-reconstructed perovskite for highly efficient and stable active-matrix light-emitting diode display | Nature Nanotechnology

Nature Nanotechnology volume 19, pages 638–645 (2024)Cite this article

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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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Liu, X. K. et al. Metal halide perovskites for light-emitting diodes. Nat. Mater. 20, 10–21 (2021).

Article CAS PubMed Google Scholar

Dey, A. et al. State of the art and prospects for halide perovskite nanocrystals. ACS Nano 15, 10775–10981 (2021).

Article CAS PubMed PubMed Central Google Scholar

Hassan, Y. et al. Ligand-engineered bandgap stability in mixed-halide perovskite LEDs. Nature 591, 72–77 (2021).

Article CAS PubMed Google Scholar

Jiang, Y. et al. Synthesis-on-substrate of quantum dot solids. Nature 612, 679–684 (2022).

Article CAS PubMed Google Scholar

Kim, J. S. et al. Ultra-bright, efficient and stable perovskite light-emitting diodes. Nature 611, 688–694 (2022).

Article CAS PubMed Google Scholar

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).

Article CAS Google Scholar

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).

Article CAS PubMed Google Scholar

Boles, M. A., Ling, D., Hyeon, T. & Talapin, D. V. The surface science of nanocrystals. Nat. Mater. 15, 141–153 (2016).

Article CAS PubMed Google Scholar

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).

Article CAS Google Scholar

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).

Article CAS PubMed Google Scholar

Shen, X. et al. Bright and efficient pure red perovskite nanocrystals light‐emitting devices via in situ modification. Adv. Funct. Mater. 32, 2110048 (2022).

Article CAS Google Scholar

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).

Article CAS Google Scholar

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).

Article CAS Google Scholar

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).

Article CAS Google Scholar

Barker, A. J. et al. Defect-assisted photoinduced halide segregation in mixed-halide perovskite thin films. ACS Energy Lett. 2, 1416–1424 (2017).

Article CAS Google Scholar

Xie, M. et al. High-efficiency pure-red perovskite quantum-dot light-emitting diodes. Nano Lett. 22, 8266–8273 (2022).

Article CAS PubMed Google Scholar

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).

Article CAS PubMed Google Scholar

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).

Article CAS Google Scholar

Chen, D. et al. Amino acid-passivated pure red CsPbI3 quantum dot LEDs. ACS Energy Lett. 8, 410–416 (2022).

Article Google Scholar

Song, Y.-H. et al. Planar defect-free pure red perovskite light-emitting diodes via metastable phase crystallization. Sci. Adv. 8, eabq2321 (2022).

Article CAS PubMed PubMed Central Google Scholar

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).

Article PubMed Google Scholar

Fiuza-Maneiro, N. et al. Ligand chemistry of inorganic lead halide perovskite nanocrystals. ACS Energy Lett. 8, 1152–1191 (2023).

Article CAS Google Scholar

Yuan, M. et al. Perovskite energy funnels for efficient light-emitting diodes. Nat. Nanotechnol. 11, 872–877 (2016).

Article CAS PubMed Google Scholar

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).

Article CAS PubMed PubMed Central Google Scholar

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).

Article CAS PubMed Google Scholar

Han, T.-H. et al. A roadmap for the commercialization of perovskite light emitters. Nat. Rev. Mater. 7, 757–777 (2022).

Article Google Scholar

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).

Article CAS PubMed PubMed Central Google Scholar

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).

Article CAS PubMed Google Scholar

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).

Article CAS Google Scholar

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).

Article CAS PubMed Google Scholar

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).

Article CAS Google Scholar

Yang, D. et al. Surface halogen compensation for robust performance enhancements of CsPbX3 perovskite quantum dots. Adv. Opt. Mater. 7, 1900276 (2019).

Article Google Scholar

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).

Article CAS PubMed PubMed Central Google Scholar

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).

Article CAS Google Scholar

Li, Y. et al. Highly luminescent and stable CsPbBr3 perovskite quantum dots modified by phosphine ligands. Nano Res. 12, 785–789 (2019).

Article CAS Google Scholar

Motti, S. G. et al. Controlling competing photochemical reactions stabilizes perovskite solar cells. Nat. Photonics 13, 532–539 (2019).

Article CAS Google Scholar

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).

Article CAS Google Scholar

Udayabhaskararao, T. et al. A mechanistic study of phase transformation in perovskite nanocrystals driven by ligand passivation. Chem. Mater. 30, 84–93 (2018).

Article CAS Google Scholar

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).

Article CAS PubMed Google Scholar

Li, C. et al. Insights into ultrafast carrier dynamics in perovskite thin films and solar cells. ACS Photonics 7, 1893–1907 (2020).

Article CAS Google Scholar

Huang, J., Yuan, Y., Shao, Y. & Yan, Y. Understanding the physical properties of hybrid perovskites for photovoltaic applications. Nat. Rev. Mater. 2, 17042 (2017).

Article CAS Google Scholar

Shen, X. et al. Zn-alloyed CsPbI3 nanocrystals for highly efficient perovskite light-emitting devices. Nano Lett. 19, 1552–1559 (2019).

Article CAS PubMed Google Scholar

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).

Article CAS Google Scholar

Zou, W. et al. Minimising efficiency roll-off in high-brightness perovskite light-emitting diodes. Nat. Commun. 9, 608 (2018).

Article PubMed PubMed Central Google Scholar

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).

Article PubMed PubMed Central Google Scholar

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).

Article CAS PubMed Google Scholar

Li, D. et al. Electronic and ionic transport dynamics in organolead halide perovskites. ACS Nano 10, 6933–6941 (2016).

Article CAS PubMed Google Scholar

Zhang, B.-B. et al. Defect proliferation in CsPbBr3 crystal induced by ion migration. Appl. Phys. Lett. 116, 063505 (2020).

Article CAS Google Scholar

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).

Article CAS Google Scholar

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).

Article CAS PubMed Google Scholar

Dai, X. et al. Solution-processed, high-performance light-emitting diodes based on quantum dots. Nature 515, 96–99 (2014).

Article CAS PubMed Google Scholar

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).

Article Google Scholar

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).

Article Google Scholar

Liu, Y. et al. Efficient blue light-emitting diodes based on quantum-confined bromide perovskite nanostructures. Nat. Photonics 13, 760–764 (2019).

Article CAS Google Scholar

Blöchl, P. E. Projector augmented-wave method. Phys. Rev. B 50, 17953–17979 (1994).

Article Google Scholar

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).

Article CAS Google Scholar

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).

Article CAS Google Scholar

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).

Article PubMed Google Scholar

Grimme, S., Ehrlich, S. & Goerigk, L. Effect of the damping function in dispersion corrected density functional theory. J. Comput. Chem. 32, 1456–1465 (2011).

Article CAS PubMed Google Scholar

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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.

School of Materials Science and Engineering, State Key Laboratory of Silicon and Advanced Semiconductor Materials, Zhejiang University, Hangzhou, People’s Republic of China

Hongjin Li, Yifeng Feng, Meiyi Zhu, Yun Gao, Chao Fan, Qiaopeng Cui, Qiuting Cai, Haiping He, Xingliang Dai, Jingyun Huang & Zhizhen Ye

Wenzhou Key Laboratory of Novel Optoelectronic and Nano Materials and Engineering Research Centre of Zhejiang Province, Institute of Wenzhou, Zhejiang University, Wenzhou, People’s Republic of China

Meiyi Zhu, Chao Fan, Haiping He, Xingliang Dai, Jingyun Huang & Zhizhen Ye

Department of Applied Physics, The Hong Kong Polytechnic University, Hong Kong, People’s Republic of China

Ke Yang

Shanxi-Zheda Institute of Advanced Materials and Chemical Engineering, Taiyuan, People’s Republic of China

Xingliang Dai & Zhizhen Ye

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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.

Correspondence to Xingliang Dai, Jingyun Huang or Zhizhen Ye.

The authors declare no competing interests.

Nature Nanotechnology thanks the anonymous reviewers for their contribution to the peer review of this work.

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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).

Source data

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.

Source data

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.

Source data

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.

Source data

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.

Source data

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.

Source data

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.

Source data

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.

Source data

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.

Source data

Supplementary Figs. 1–18 and Tables 1–5.

HI injection into the OA reaction system.

HI injection into the DSPA reaction system.

Independently controllable emission of active-matrix displays.

Statistical source data.

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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. 19, 638–645 (2024). https://doi.org/10.1038/s41565-024-01652-y

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Received: 20 July 2023

Accepted: 13 March 2024

Published: 22 April 2024

Issue Date: May 2024

DOI: https://doi.org/10.1038/s41565-024-01652-y

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