Abstract
Light-emitting diodes (LEDs) are ubiquitous in modern society, with applications spanning from lighting and displays to medical diagnostics and data communications. Metal-halide perovskites are promising materials for LEDs because of their excellent optoelectronic properties and solution processability. Although research has progressed substantially in optimizing their external quantum efficiency, the modulation characteristics of perovskite LEDs remain unclear. Here we report a holistic approach for realizing fast perovskite photonic sources on silicon based on tailoring alkylammonium cations in perovskite systems. We reveal the recombination behaviour of charged species at various carrier density regimes relevant for their modulation performance. By integrating a Fabry–Pérot microcavity on silicon, we demonstrate perovskite devices with efficient light outcoupling. We achieve device modulation bandwidths of up to 42.6 MHz and data rates above 50 Mbps, with further analysis suggesting that the bandwidth may exceed gigahertz levels. The principles developed here will support the development of perovskite light sources for next-generation data-communication architectures. The demonstration of solution-processed perovskite emitters on silicon substrates also opens up the possibility of integration with micro-electronics platforms.
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Acknowledgements
This work was supported by the National Key Research and Development Program of China (2021YFA1401100), the National Natural Science Foundation of China (61901268 and 52202165), the ‘111 Project’ (B20030), the Fundamental Research Funds for the Central Universities (ZYGX2019Z018), the Innovation Group Project of Sichuan Province (20CXTD0090), the UESTC Shared Research Facilities of Electromagnetic Wave and Matter Interaction (Y0301901290100201) and EPSRC (2015, EP/M015165/1; 2021, EP/V048732/1; 2016, EP/N010825/1; 2021, EP/V061747/1). W.Z. acknowledges an EPSRC New Investigator Award (2018, EP/R043272/1) and the Newton Advanced Fellowship (192097) for financial support. L.D. thanks the Cambridge Trust and the China Scholarship Council for funding. E.B.-C. thanks the EPSRC for a studentship, and H.W. thanks G. Ren for support.
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Contributions
I.H.W. initially proposed the project. J.W., Q.C., H.J.S. and W.Z. conceived the project and supervised the project, together with S.J.S., A.R., N.C.G., Y.L., R.H.F., R.V.P. and I.H.W. A.R. and H.W. conducted the experiments and coordinated the collaboration and were assisted by J.W., Q.C., H.J.S. and W.Z. A.R. and H.W. developed the perovskite films and devices. J.Y., Z.L. and A.R. performed the PLQE and analysed the data. A.R. and H.W. performed the absorption and photoluminescence measurements. L.Y., A.R. and H.W. wrote the computational codes and performed the Elliott modelling. S.A.H and A.M.S. performed the SEM and TEM. M.T. performed the AFM. X. Liu, J.B. and B.L. performed the XRD and GIXRD measurements and analysed the data. J.A.S. performed the GIWAXS measurements and analysed the data. J.X. and C.Y. performed optical modelling and J.X., A.R. and H.W. analysed the data. A.R., H.W., S.Z. and I.P.M. performed the device emission performance measurements and analysed the data. H.L. and F.F. performed the ToF-SIMS and thermal admittance spectroscopy and analysed the data. H.W., R.C., H.Y., J.H. and A.W. provided the data-transmission set-ups. H.W. performed the device modulation bandwidth measurements and A.R. and H.W. analysed the data. X.B. and Z.L. performed the TRPL and X.B. and A.R. analysed the data. E.B.-C. and J.L.-H. performed the OPTP and E.B.-C., J.L.-H., A.R. and H.W. analysed the data. L.D. performed the TA and data analysis under the supervision of N.C.G. H.W. and X. Li performed the data-transmission and signal-processing measurements and analysed the data. S.K. performed the DFT simulations. A.R. and H.W. drafted the first version of the paper, with assistance from J.W., Q.C., H.J.S. and W.Z. All authors read and commented upon, or contributed to the writing of, the paper.
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H.J.S. is a co-founder of Oxford PV, which is commercializing perovskite-based photovoltaics. H.J.S. and R.H.F. are co-founders of Helio Display Materials, which is commercializing perovskite materials for light-emitting applications. The other authors declare no competing interests.
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Extended data
Extended Data Fig. 1 Photoluminescence (PL) properties of the perovskite films.
a-c, PL maps of the perovskite films modified with MABr (a), PEABr (b) and t-BABr (c) as a function of the molar ratio of the organic cation and photon energy. The emission features (b) of n = 2 and n = 3 indicate the quasi-2D phases. The blue shifts of the PL emission and absorption onsets can be observed as the molar ratio of PEABr is increased. The PL peaks slightly shift with the increase of t-BABr but no quasi-2D features are appeared, even at a high concentration (x = 1.0). Logarithmic-PL spectra are used to plot maps in the linear scale.
Extended Data Fig. 2 X-ray diffraction (XRD) and grazing-incidence wide-angle X-ray scattering (GIWAXS) characterisations.
a, XRD patterns of the control, MA, PEA, t-BA films deposited on silicon substrates. The asterisk symbols denote the peaks of silicon. The perovskite reflections in the XRD pattern from the MA film are shifted to lower angles suggesting some MA+ incorporation into the A-site of the 3D perovskite phase. The additional peaks for the MA film are assigned to Cs4PbBr6, which are also present in the PEA film. The broad, weak perovskite diffraction peaks from the PEA film indicate the reduced perovskite crystallinity along the measurement axis. b, Grazing-incidence XRD patterns of the control, MA, PEA, t-BA films in the 2θ range of 8°-23.5°. c-f, GIWAXS patterns of the control (c), MA (d), PEA (e), t-BA (f) films deposited on silicon substrates. With the control and MA films, isotropic Debye-Scherrer scattering rings are observed, indicating grains are randomly oriented, as is typical for neat CsPbBr3. With the larger alkylammonium cations, two different CsPbBr3 texture directions are dominant. GIWAXS measurements further reveal that Cs4PbBr6 is present to some extent in all films (Supplementary Fig. 10, 11), and in the MA and t-BA samples the Cs4PbBr6 phase exhibits strong orientation. We infer from these data that the t-BA film exhibits optimal crystallinity, and uniquely benefits from both CsPbBr3 and Cs4PbBr6 domains being highly oriented.
Extended Data Fig. 3 Transmission electron microscopy (TEM) and elemental distribution analysis.
a, b, Cross-sectional scanning transmission electron microscopy (STEM) image (a) and Energy dispersive spectroscopy (EDS) map (b) of the optimised t-BA device. c, Elemental distribution maps of the selected area. Scale bar, 50 nm.
Extended Data Fig. 4 Time-of-flight secondary ion mass spectrometry (ToF-SIMS) depth analysis of the aged devices.
a, Elemental depth profiles of the aged t-BA devices without (a) and with (b) polystyrene (PS) layer after 20 hours of continuous operation.
Extended Data Fig. 5 Light outcoupling and power dissipation analysis.
a-b, Simulated cross-sectional view of the normalised power intensity distributions of the devices with a Fabry–Pérot microcavity. An isotropic dipole source is centred in the perovskite emissive layer at the emission wavelength of 530 nm. The dipole sources are placed in the centre of the perovskite layer with a horizontal orientation px/y (a) and a vertical orientation pz (b). x-z plane is as the plane of incidence. c, Normalised radiated power density spectra of the devices at different view angles. d, Simulated (solid lines) and measured (solid symbols) angular EL profiles of the devices with the different perovskite emitters.
Extended Data Fig. 6 Frequency response characteristics.
a–d, Size-dependent frequency response of the control (a), MA (b), PEA (c) and t-BA (d) devices with an applied voltage of 6.5 V. e-h, Voltage-dependent frequency response of the control (e), MA (f), PEA (g) and t-BA (h) devices (0.028 mm2).
Extended Data Fig. 7 Femtosecond optical pump terahertz probe (OPTP) spectroscopy.
a-d, OPTP transients of the control (a), MA (b), PEA (c) and t-BA (d) films measured after an excitation with a 410 nm pump pulse (50 fs duration) at various fluences. Solid lines are the rate equation fits to the fluence-dependent transients (Supplementary Note 6). Error bars represent the standard error obtained from eight independent measurements (n = 8). e-h, Derived effective THz mobilities φ∑μ of the control (e), MA (f), PEA (g) and t-BA (h) films at early times (0–10 ps). Error bars represent the standard error obtained from eight independent measurements (n = 8).
Extended Data Fig. 8 Thermal admittance spectra.
a–d, Capacitance-frequency spectra of the control (a), MA (b), PEA (c) and t-BA (d) devices measured with the probe frequencies from 20 Hz to 2 MHz in the temperature range of 208–298 K with a step size of 10 K. e-h, Derived differential capacitance spectra as a function of the probe frequency for the control (e), MA (f), PEA (g) and t-BA (h) devices. i, Arrhenius plots of characteristic frequencies of the trap peaks (black circles in differential capacitance spectra e-h). EA denotes the main defect energy level within the perovskite layers. j, Mott–Schottky characteristics for extracting the build-in potential Vbi and the depletion width W.
Extended Data Fig. 9 Transient absorption (TA) spectroscopy.
a–h, TA maps and spectra at the selected timescales (0.3–1500 ps) of the control (a, e), MA (b, f), PEA (c, g) and t-BA (d, h) films with a 400 nm pump. Dominated ground state-bleaches are assigned to 3D phase of the control, MA and t-BA films. The characteristic quasi-2D/3D ground state-bleaches are assigned to n = 1, 2, 3, 4, ≥5 of the PEA films. TA spectra probed at the selected wavelengths corresponding to the distinct bleaching lines (n = 1, 2, 3, 4, ≥5) as a function of the delay time (Supplementary Fig. 38). i-l, Bleaching dynamics under various fluences of the control (i), MA (j), PEA (k) and t-BA (l) films monitored near the absorption onsets. m-p, Logarithmic recombination rate −dn/dt as a function of the carrier density n for the control, MA, PEA, t-BA films, respectively. The data points are extracted from the fluence-dependent dynamics with the initial charge carrier density n0 (Supplementary Note 5). Different orders of the recombination rate dn(t)/dt with n indicates the transitions between monomolecular, bimolecular and Auger recombination pathways according to the rate equation. Dash lines in m-p indicate the 95% confidence bounds for each fitting.
Extended Data Fig. 10 Data transmission performance.
a, Modulation bandwidth vs. data rate for the control, MA, PEA and t-BA devices. The data rates are defined at a bit error rate (BER) close to the 7% forward error correction threshold of 3.8 × 10−3. The data points of each colour are collected from 10 devices. Scatter plots are presented as mean values with error bars indicating the standard errors of the mean. Shaded areas indicate the 95% prediction interval for each linear fitting. b-d, Eye diagram demonstrations of a t-BA device (0.028 mm2) measured at the data rates of 20 Mbps (b), 50 Mbps (c) and 80 Mbps (d) with a 1.5 mA DC bias, corresponding to a BER of 1.5 × 10−5, 2.2 × 10−3 and 1.0 × 10−2, respectively. The t-BA device displays clear open eye diagrams up to 50 Mbps data rate and degrades when the baud rate increased to 80 Mbps.
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Supplementary Notes 1–7, Figs. 1–38 and References.
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Ren, A., Wang, H., Dai, L. et al. High-bandwidth perovskite photonic sources on silicon. Nat. Photon. 17, 798–805 (2023). https://doi.org/10.1038/s41566-023-01242-9
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DOI: https://doi.org/10.1038/s41566-023-01242-9
