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Ultrastable near-infrared perovskite light-emitting diodes

Abstract

Perovskite light-emitting diodes are an emerging light source technology. However, similar to perovskite solar cells, poor operational stability remains an obstacle for commercial applications. Here we demonstrate ultrastable and efficient near-infrared (~800 nm) perovskite light-emitting diodes with record-long operational lifetimes (T50, extrapolated) of 11,539 h (~1.3 years) and 32,675 h (~3.7 years) for initial radiance (or current densities) of 3.7 W sr−1 m−2 (~5.0 mA cm−2) and 2.1 W sr−1 m−2 (~3.2 mA cm−2), respectively, with even longer lifetimes forecasted for lower radiance. Key to this stability is the introduction of a dipolar molecular stabilizer, which interacts with the cations and anions at the perovskite grain boundaries. This suppresses ion migration under electric fields, preventing the formation of lead iodide, which mediates the phase transformation and decomposition of α-FAPbI3 perovskite. These results remove the critical concern that halide perovskite devices may be intrinsically unstable, paving the path towards industrial applications.

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Fig. 1: Structure and performance of PeLEDs.
Fig. 2: Structural and PL stability measurements of perovskite samples.
Fig. 3: Characterization of chemical interactions in SFB10-treated samples.
Fig. 4: Current–voltage scans of PeLEDs and microscopic PL imaging of perovskite samples.

Data availability

The main data supporting the findings of this study are available within the Article and its Supplementary Information. Extra data are available from the corresponding authors upon reasonable request.

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Acknowledgements

This work was supported by the National Key R&D Program of China (grant no. 2018YFB2200401) (D.D.), the National Natural Science Foundation of China (NSFC) (61975180 (D.D.), 62005243 (B.Z.), 62005230 (M.C.), 61974126 and 51902273 (C.L.) and 52102177 (W.L.)), Kun-Peng Programme of Zhejiang Province (D.D.), Natural Science Foundation of Zhejiang Province (LR21F050003) (B.Z.), Natural Science Foundation of Fujian Province (2021J06009) (C.L.), Natural Science Foundation of Jiangsu Province (BK20210313) (W.L.), Top-Notch Academic Programs Project of Jiangsu Higher Education Institutions (TAPP) (W.L.), Jiangsu Specially-Appointed Professor Program (W.L.), Fundamental Research Funds for the Central Universities (2020QNA5002 (B.Z.), 2021FZZX001–08 (Z.H.), and 20720200086 and 20720210088 (M.C.)) and Zhejiang University Education Foundation Global Partnership Fund (D.D.). We are grateful to M. Yu and Y. Zhao for their administrative support. We acknowledge the technical support from the Core Facilities, State Key Laboratory of Modern Optical Instrumentation, Zhejiang University. This work was supported by the College of Optical Science and Engineering (Zhejiang University), which celebrates its 70th anniversary in 2022.

Author information

Authors and Affiliations

Authors

Contributions

B.G. planned the experiments under the guidance of D.D. and B.Z. B.G. designed and fabricated the highly stable and efficient PeLEDs and carried out the device characterization and data analyses. B.G. and R.L. performed the TCSPC measurements. R.L. performed the TA experiments. S.J. and P.L. conducted the microscopic luminescence imaging experiments under the supervision of C.L. and M.C. Z.R. assisted with the preparation of samples and experimental setups for the device stability tests. L.Z. carried out the DFT calculations under Z.H.’s supervision. X.C. and B.G. performed the angular-emission profile measurements. B.G., B.Z. and D.D. wrote the initial manuscript, with useful inputs from Y.L. All the authors contributed to the work and commented on the paper.

Corresponding authors

Correspondence to Baodan Zhao or Dawei Di.

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Competing interests

D.D., B.G., Y.L. and B.Z. are inventors on CN patent application no. 202111447766.0. The remaining authors declare no competing interests.

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Nature Photonics thanks Yasser Hassan, Haibo Zeng and Michele Saba for their contribution to the peer review of this work.

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Extended data

Extended Data Fig. 1 HAADF-STEM images and EDS composite mapping of SFB10-based perovskite devices.

a, Cross-sectional HAADF-STEM image of a SFB10-stabilized device. Scale bar: 100 nm. b, Cross-sectional HAADF-STEM image of a SFB10-stabilized sample. Scale bar: 2 nm. The lattice spacings (10 fringes) show agreement with the cubic α-phase of FAPbI3. c, EDS elemental maps of the SFB10-stabilized perovskite device. Scale bar: 50 nm.

Extended Data Fig. 2 Further performance data of control and SFB10-based PeLEDs.

a, Current density-voltage characteristics. Inset shows the EL spectra of PeLEDs with different SFB10 content. b, Radiance-voltage characteristics. c, EQE-current density characteristics. d, EQE histograms for control and SFB10-based PeLEDs. e, Angular emission profile of SFB10-based PeLEDs. f, The radiance-current density relationship determined from the averaged results of 10 representative devices.

Extended Data Fig. 3 Spectral stability measurements of SFB10-stabilized PeLEDs.

a, EL spectrum of a SFB10-stabilized device measured after 2000 h aging under 10 mA cm−2. b, EL spectrum of a SFB10-stabilized device measured after 450 h aging under 20 mA cm−2. c, EL spectrum of a SFB10-stabilized device measured after 114 h aging under 50 mA cm−2. d, EL spectrum of a SFB10-stabilized device measured after 68 h aging under 100 mA cm−2. e, EL spectrum of a SFB10-stabilized device measured after 22.4 h aging under 200 mA cm−2. f, EL spectra of SFB10-stabilized PeLEDs before and after aging tests.

Extended Data Fig. 4 Accelerated aging tests in humid air (70–75% RH, 20 ± 5 °C) for SFB10-stabilized PeLEDs with and without encapsulation.

a, Accelerated aging tests for encapsulated devices at different current densities. b, Accelerated aging tests for unencapsulated devices at different current densities. c, The T50 lifetimes as a function of initial radiance (R0) for encapsulated devices, the dash line is the fitting of T50 data to equation R0n × T50 = constant, where n is the acceleration factor (n = 2.10). d, The T50 lifetimes as a function of initial radiance (R0) for unencapsulated devices. The acceleration factor (n) is 1.89.

Extended Data Fig. 5 Morphological characterization for control and SFB10-stabilized samples.

a, SEM image of the control samples. Scale bar: 500 nm. b, SEM image of SFB10-stabilized samples. Scale bar: 500 nm. c, AFM image of the control samples. Scale bar: 1 μm. d, AFM image of SFB10-stabilized samples. Scale bar: 1 μm.

Extended Data Fig. 6 Additional optical and electrical characterizations for control and SFB10-stabilized samples.

a, Absorbance and PL spectra of the perovskite films. b, Transient absorption (TA) spectra of a SFB10-stabilized sample. c, The TA dynamics probed at 790 nm. d, PL decay curves of the perovskite films (excitation fluence: 20 nJ cm−2). e, The current-voltage characteristics of an electron-only device based on the control sample. f, The current-voltage characteristics of an electron-only device based on SFB10-stabilized perovskite. The device structure was glass/ITO/ZnO/PEIE/perovskite/TPBi/LiF/Al.

Extended Data Fig. 7 Additional optical measurements and sample appearance of SFB10-stabilized FAPbI3, pristine FAPbI3, SFB10-treated PbI2, and pristine PbI2.

a, Absorption spectra of PbI2 and PbI2:SFB10 samples. The molar ratio of SFB10 to PbI2 was 1:1. Inset: photos of pristine PbI2 and SFB10-treated PbI2 samples after annealing. b, PL spectra of control and SFB10-stabilized samples before annealing. Inset: photos of control and SFB10-stabilized perovskite samples before annealing.

Extended Data Fig. 8 XPS measurements of SFB10-stabilized FAPbI3, pristine FAPbI3, SFB10-treated PbI2, and pristine PbI2.

a, S 2p; b, N 1s; c, O 1s; d, C 1s spectra of samples for SFB10-stabilized FAPbI3, pristine FAPbI3, SFB10-treared PbI2 and pristine PbI2. The XPS spectra were calibrated with C 1s peak at 284.8 eV. e, The atomic ratio of I/Pb on the surfaces of the control and SFB10-stabilized perovskite samples. f, The atomic ratio of N(FA)/Pb on the surfaces of the control and SFB10-stabilized perovskite samples.

Extended Data Fig. 9 Additional liquid-state NMR characterization.

a, 207Pb NMR spectra of FAPbI3: SFB10 and FAPbI3 precursors dissolved in DMSO-d6. b-c, 1H NMR spectra of FAPbI3: SFB10 films and SFB10 dissolved in DMSO-d6.

Extended Data Fig. 10 DFT analyses.

a, Surface configuration after relaxation. The SFB10 molecule tends to lie on the surface with a -SO3 group close to the Pb atom. The long carbon chain of SFB10 extends along the perovskite crystal surface. The chemical bonding between Pb and O can be observed with a binding energy of −0.41 eV. b, Differential charge density plot (isosurface value of 0.0015 e/Å; charge accumulation/depletion is plotted in yellow/cyan) for the equilibrium structure, showing that the bonding between the O and Pb atoms also induces charge redistribution on the -SO3 group, Pb atom and partially along the carbon chain, further confirming the strong chemical interactions between the SFB10 molecule and FAPbI3 crystal surfaces. The long carbon chain of SFB10 extends along the perovskite crystal surface. This could enhance the surface stability and increase the barrier to ion migration perpendicular to the perovskite crystal surface.

Supplementary information

Supplementary Information

Supplementary Fig. 1.

Supplementary Video 1

Time-dependent PL imaging of a control sample under an external electric field (~3 × 104 V m−1).

Supplementary Video 2

Time-dependent PL imaging of an SFB10-stabilized sample under an external electric field (~3 × 104 V m−1).

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Guo, B., Lai, R., Jiang, S. et al. Ultrastable near-infrared perovskite light-emitting diodes. Nat. Photon. 16, 637–643 (2022). https://doi.org/10.1038/s41566-022-01046-3

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