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Sub-millimetre light detection and ranging using perovskites

Nature Electronics volume 5, pages 511–518 (2022)Cite this article

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Abstract

Light detection and ranging (LiDAR) technology is an active remote-sensing system used in autonomous vehicles, machine vision and augmented reality. Improvements in the speed and signal-to-noise ratio of photodetectors are needed to meet these demanding ranging applications. Silicon electronics have been the principal option for LiDAR photodetectors in the range of 850–950 nm. However, its indirect bandgap leads to a low absorption coefficient in the near-infrared region, as well as a consequent trade-off between speed and efficiency. Here we report solution-processed lead–tin binary perovskite photodetectors that have an external quantum efficiency of 85% at 850 nm, dark current below 10–8 A cm–2 and response time faster than 100 ps. The devices are fabricated using self-limiting and self-reduced tin precursors that enable perovskite crystallization at the desired stoichiometry and prevent the formation of interfacial defects with the hole transport layer. The approach removes oxygen from the solution, converts Sn4+ to Sn2+ through comproportionation, and leaves neither metallic tin nor SnOx residues. To illustrate the potential of these solution-processed perovskite photodetectors in LiDAR, we show that they can resolve sub-millimetre distances with a typical 50 µm standard deviation.

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Fig. 1: Si and Pb–Sn photodetectors.
Fig. 2: Reducing strategy for Sn precursor.
Fig. 3: Performance of Pb–Sn photodetectors.
Fig. 4: Speed measurements for Pb–Sn devices.
Fig. 5: ToF measurements.

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Data availability

The datasets generated during and/or analysed during the current study are available from the corresponding author on reasonable request.

References

  1. Royo, S. & Ballesta-Garcia, M. An overview of LiDAR imaging systems for autonomous vehicles. Appl. Sci. 9, 4093 (2019).

  2. Behroozpour, B., Sandborn, P. A. M., Wu, M. C. & Boser, B. E. LiDAR system architectures and circuits. IEEE Commun. Mag. 55, 135–142 (2017).

    Article  Google Scholar 

  3. Yatsui, T. et al. Enhanced photo-sensitivity in a Si photodetector using a near-field assisted excitation. Commun. Phys. 2, 62 (2019).

  4. Noffsinger, J., Kioupakis, E., Walle, C. G., Van de, Louie, S. G. & Cohen, M. L. Phonon-assisted optical absorption in silicon from first principles. Phys. Rev. Lett. 108, 167402 (2012).

    Article  Google Scholar 

  5. Meredith, P. & Armin, A. Scaling of next generation solution processed organic and perovskite solar cells. Nat. Commun. 9, 5261 (2018).

  6. Fu, F. et al. High-efficiency inverted semi-transparent planar perovskite solar cells in substrate configuration. Nat. Energy 2, 16190 (2016).

    Article  Google Scholar 

  7. Kim, Y. C. et al. Printable organometallic perovskite enables large-area, low-dose X-ray imaging. Nature 550, 87–91 (2017).

    Article  Google Scholar 

  8. Saliba, M., Correa-Baena, J.-P., Grätzel, M., Hagfeldt, A. & Abate, A. Perovskite solar cells: from the atomic level to film quality and device performance. Angew. Chem. Int. Ed. 57, 2554–2569 (2018).

    Article  Google Scholar 

  9. García De Arquer, F. P., Armin, A., Meredith, P. & Sargent, E. H. Solution-processed semiconductors for next-generation photodetectors. Nat. Rev. Mater. 2, 16100 (2017).

    Article  Google Scholar 

  10. Zhou, J. et al. Lead-free perovskite derivative Cs2SnCl6−xBrx single crystals for narrowband photodetectors. Adv. Opt. Mater. 7, 1900139 (2019).

    Article  Google Scholar 

  11. Stranks, S. D. et al. Electron-hole diffusion lengths exceeding 1 micrometer in an organometal trihalide perovskite absorber. Science 342, 341–344 (2013).

    Article  Google Scholar 

  12. Fu, Y. et al. Metal halide perovskite nanostructures for optoelectronic applications and the study of physical properties. Nat. Rev. Mater. 4, 169–188 (2019).

    Article  Google Scholar 

  13. Correa-Baena, J.-P. et al. Promises and challenges of perovskite solar cells. Science 358, 739–744 (2017).

    Article  Google Scholar 

  14. Dou, L. et al. Solution-processed hybrid perovskite photodetectors with high detectivity. Nat. Commun. 5, 5404 (2014).

    Article  Google Scholar 

  15. Werner, J. et al. Improving low-bandgap tin–lead perovskite solar cells via contact engineering and gas quench processing. ACS Energy Lett. 5, 1215–1223 (2020).

    Article  Google Scholar 

  16. Lin, R. et al. Monolithic all-perovskite tandem solar cells with 24.8% efficiency exploiting comproportionation to suppress Sn(ii) oxidation in precursor ink. Nat. Energy 4, 864–873 (2019).

    Article  Google Scholar 

  17. Prasanna, R. et al. Design of low bandgap tin–lead halide perovskite solar cells to achieve thermal, atmospheric and operational stability. Nat. Energy 4, 939–947 (2019).

    Article  Google Scholar 

  18. Lee, S., Ha, T. J. & Kang, D. W. Mixed-halide Pb-Sn binary perovskite films with various Sn-content for Pb-reduced solar cells. Mater. Lett. 227, 311–314 (2018).

    Article  Google Scholar 

  19. Jiang, T. et al. Realizing high efficiency over 20% of low-bandgap Pb–Sn-alloyed perovskite solar cells by in situ reduction of Sn4+. Sol. RRL 4, 1900467 (2020).

    Article  Google Scholar 

  20. Ghimire, N. et al. Mitigating open-circuit voltage loss in Pb–Sn low-bandgap perovskite solar cells via additive engineering. ACS Appl. Energy Mater. 4, 1731–1742 (2021).

    Article  Google Scholar 

  21. Tai, Q. et al. Antioxidant grain passivation for air-stable tin-based perovskite solar cells. Angew. Chem. Int. Ed. 58, 806–810 (2019).

    Article  Google Scholar 

  22. Ma, L. et al. Carrier diffusion lengths of over 500 nm in lead-free perovskite CH3NH3SnI3 films. J. Am. Chem. Soc. 138, 14750–14755 (2016).

    Article  Google Scholar 

  23. Lee, S. J. et al. Fabrication of efficient formamidinium tin iodide perovskite solar cells through SnF2–pyrazine complex. J. Am. Chem. Soc. 138, 3974–3977 (2016).

    Article  Google Scholar 

  24. Liao, W. et al. Lead-free inverted planar formamidinium tin triiodide perovskite solar cells achieving power conversion efficiencies up to 6.22%. Adv. Mater. 28, 9333–9340 (2016).

    Article  Google Scholar 

  25. Konstantakou, M. & Stergiopoulos, T. A critical review on tin halide perovskite solar cells. J. Mater. Chem. A 5, 11518–11549 (2017).

    Article  Google Scholar 

  26. Ke, W. et al. Ethylenediammonium-based ‘hollow’ Pb/Sn perovskites with ideal band gap yield solar cells with higher efficiency and stability. J. Am. Chem. Soc. 141, 8627–8637 (2019).

  27. Xiao, K. et al. All-perovskite tandem solar cells with 24.2% certified efficiency and area over 1 cm2 using surface-anchoring zwitterionic antioxidant. Nat. Energy 5, 870–880 (2020).

    Article  Google Scholar 

  28. Gu, F. et al. Improving performance of lead-free formamidinium tin triiodide perovskite solar cells by tin source purification. Sol. RRL 2, 1800136 (2018).

    Article  Google Scholar 

  29. Zhang, J. et al. Solution-processed Sr-doped NiOx as hole transport layer for efficient and stable perovskite solar cells. Sol. Energy 174, 1133–1141 (2018).

    Article  Google Scholar 

  30. Liu, A. et al. Hole mobility modulation of solution-processed nickel oxide thin-film transistor based on high-k dielectric. Appl. Phys. Lett. 108, 233506 (2016).

    Article  Google Scholar 

  31. Kung, P.-K. et al. A review of inorganic hole transport materials for perovskite solar cells. Adv. Mater. Interfaces 5, 1800882 (2018).

    Article  Google Scholar 

  32. Chang, C.-C., Tao, J.-H., Tsai, C.-E., Cheng, Y.-J. & Hsu, C.-S. Cross-linked triarylamine-based hole-transporting layer for solution-processed PEDOT:PSS-free inverted perovskite solar cells. ACS Appl. Mater. Interfaces 10, 21466–21471 (2018).

    Article  Google Scholar 

  33. Chi, D. et al. Composition and interface engineering for efficient and thermally stable Pb–Sn mixed low-bandgap perovskite solar cells. Adv. Funct. Mater. 28, 1804603 (2018).

    Article  Google Scholar 

  34. Jeng, J.-Y. et al. Nickel oxide electrode interlayer in CH3NH3PbI3 perovskite/PCBM planar-heterojunction hybrid solar cells. Adv. Mater. 26, 4107–4113 (2014).

    Article  Google Scholar 

  35. You, J. et al. Improved air stability of perovskite solar cells via solution-processed metal oxide transport layers. Nat. Nanotechnol. 11, 75–81 (2015).

    Article  Google Scholar 

  36. Fang, Z., Xiao, K. & Tan, H. Low-temperature processed inorganic hole transport layer for efficient and stable mixed Pb-Sn low-bandgap perovskite solar cells. Sci. Bull. 64, 1399 (2019).

  37. Lee, S. J. et al. Reducing carrier density in formamidinium tin perovskites and its beneficial effects on stability and efficiency of perovskite solar cells. ACS Energy Lett. 3, 46–53 (2017).

    Article  Google Scholar 

  38. Diau, E. W.-G., Jokar, E. & Rameez, M. Strategies to improve performance and stability for tin-based perovskite solar cells. ACS Energy Lett. 4, 1930–1937 (2019).

    Article  Google Scholar 

  39. Lin, Q., Armin, A., Nagiri, R. C. R., Burn, P. L. & Meredith, P. Electro-optics of perovskite solar cells. Nat. Photon. 9, 106–112 (2014).

    Article  Google Scholar 

  40. Walsh, A. & Stranks, S. D. Taking control of ion transport in halide perovskite solar cells. ACS Energy Lett. 3, 1983–1990 (2018).

    Article  Google Scholar 

  41. Hauff, Evon Impedance spectroscopy for emerging photovoltaics. J. Phys. Chem. C 123, 11329–11346 (2019).

    Article  Google Scholar 

  42. Shi, J. et al. From ultrafast to ultraslow: charge-carrier dynamics of perovskite solar cells. Joule 2, 879–901 (2018).

    Article  Google Scholar 

  43. Zarazua, I. et al. Surface recombination and collection efficiency in perovskite solar cells from impedance analysis. J. Phys. Chem. Lett. 7, 5105–5113 (2016).

    Article  Google Scholar 

  44. Mahmood, K., Sarwar, S. & Mehran, M. T. Current status of electron transport layers in perovskite solar cells: materials and properties. RSC Adv. 7, 17044–17062 (2017).

    Article  Google Scholar 

  45. Brandt, R. E., Stevanović, V., Ginley, D. S. & Buonassisi, T. Identifying defect-tolerant semiconductors with high minority-carrier lifetimes: beyond hybrid lead halide perovskites. MRS Commun. 5, 265–275 (2015).

    Article  Google Scholar 

  46. Blum, V. et al. Ab initio molecular simulations with numeric atom-centered orbitals. Comput. Phys. Commun. 180, 2175–2196 (2009).

    Article  MATH  Google Scholar 

  47. Havu, V., Blum, V., Havu, P. & Scheffler, M. Efficient O(N) integration for all-electron electronic structure calculation using numeric basis functions. J. Comput. Phys. 228, 8367–8379 (2009).

    Article  MATH  Google Scholar 

  48. Ren, X. et al. Resolution-of-identity approach to Hartree–Fock, hybrid density functionals, RPA, MP2 and GW with numeric atom-centered orbital basis functions. New J. Phys. 14, 053020 (2012).

    Article  Google Scholar 

  49. Weston, L., Tailor, H., Krishnaswamy, K., Bjaalie, L. & Van de Walle, C. G. Accurate and efficient band-offset calculations from density functional theory. Comput. Mater. Sci. 151, 174–180 (2018).

    Article  Google Scholar 

  50. Li, C. et al. Ultrafast and broadband photodetectors based on a perovskite/organic bulk heterojunction for large-dynamic-range imaging. Light Sci. Appl. 9, 31 (2020).

    Article  Google Scholar 

  51. Zheng, T. et al. Polymer: fullerene bimolecular crystals for near-infrared spectroscopic photodetectors. Adv. Mater. 29, 1702184 (2017).

  52. Yao, Y. et al. Plastic near-infrared photodetectors utilizing low band gap polymer. Adv. Mater. 19, 3979–3983 (2007).

    Article  Google Scholar 

  53. Kim, J. Y. et al. Single-step fabrication of quantum funnels via centrifugal colloidal casting of nanoparticle films. Nat. Commun. 6, 7772 (2015).

  54. Wang, W. et al. Highly sensitive low-bandgap perovskite photodetectors with response from ultraviolet to the near-infrared region. Adv. Funct. Mater. 27, 1703953 (2017).

  55. Shen, L. et al. Integration of perovskite and polymer photoactive layers to produce ultrafast response, ultraviolet-to-near-infrared, sensitive photodetectors. Mater. Horiz. 4, 242–248 (2017).

    Article  Google Scholar 

  56. Clifford, J. P. et al. Fast, sensitive and spectrally tuneable colloidal-quantum-dot photodetectors. Nat. Nanotechnol. 4, 40–44 (2009).

    Article  Google Scholar 

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Acknowledgements

This work was supported by the Natural Sciences and Engineering Research Council (NSERC) Alexander Graham Bell Canada Graduate Scholarships (CGS-D), Materials for Enhanced Energy Technologies (MEET) scholarships and the NSERC Collaborative Research and Training Experience (CREATE) program (grant no. 466083). F.P.G.A. acknowledges funding from CEX2019- 000910-S (MCIN/ AEI/10.13039/501100011033), Fundació Cellex, Fundació Mir-Puig, Generalitat de Catalunya through CERCA.

Author information

Author notes

  1. Makhsud I. Saidaminov

    Present address: Department of Chemistry, University of Victoria, Victoria, British Columbia, Canada

  2. These authors contributed equally: Amin Morteza Najarian, Maral Vafaie.

Authors and Affiliations

  1. The Edward S. Rogers Department of Electrical and Computer Engineering, University of Toronto, Toronto, Ontario, Canada

    Amin Morteza Najarian PhD, Maral Vafaie, Andrew Johnston, Tong Zhu, Mingyang Wei, Makhsud I. Saidaminov, Yi Hou, Sjoerd Hoogland & Edward H. Sargent

  2. ICFO–Institut de Ciències Fotòniques, The Barcelona Institute of Science and Technology, Barcelona, Spain

    F. Pelayo García de Arquer

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Contributions

A.M.N., F.P.G.A. and E.H.S. conceived the idea and designed the experiments. M.W. contributed to the initial fabrication and speed measurements. A.M.N. and M.V. modelled the device performance and also fabricated the devices. M.V. measured the EQE and dark current of the device. A.M.N. performed the TPC measurement and LiDAR demo. T.Z. performed the theoretical calculation for SnOx energy level. E.H.S., S.H., M.I.S. and Y.H. provided advice. A.M.N., A.J., M.V., F.P.G.A. and E.H.S. composed the manuscript. All the authors discussed the results and commented on the manuscript.

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Correspondence to Amin Morteza Najarian PhD or Edward H. Sargent.

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Extended data

Extended Data Fig. 1 Performance modeling of the photodetector.

Equations are provided in Methods section. a, Percentage of absorbed light vs. thickness at indicated absorption coefficients. EQE and bandwidth of b, Silicon and c, PbSn perovskite vs. film thickness. d, Comparison of silicon and PbSn perovskite from the last two panels. Parameters used for the modeling are given in Extended Data Fig. 2a.

Extended Data Fig. 2 Combined speed × efficiency characteristic of the photodetector.

a, Parameters used in the modeling of PbSn and Silicon photodetectors. b, Combined speed × efficiency modeling of silicon and PbSn PVK. c, Comparison between estimated performance and actual devices.

Extended Data Fig. 3 Performance of NiOx vs PEDOT:PSS HTL.

a, EQE comparison between PEDOT:PSS and NiOx using tin-powder reduced precursor (TPRP) strategy. b, Representative current density vs. voltage (JV curves) under the dark condition for the mentioned HTLs. Tin wire-reduced precursor strategy is used for all three shown cases. c, Comparison of dark current density at 50 mV for devices fabricated with PEDOT:PSS, NiOx, and without HTL with different Sn reducing strategy.

Extended Data Fig. 4 Possibility of interfacial SnOx formation.

a, Diagram comparing the formation energy of different form of oxide for Ni and Sn. Electrostatic potential (in eV) at the cores of oxygen atoms along the longitudinal direction of the b, DFT simulated structure of formed SnO layer on top of NiO HTL. c, NiO/SnO (001) and d, NiO/SnO2 (001) longitudinally lattice-matched supercell calculated by DFT-PBE within spin-polarized treatment for Ni. In each subplot, the top are the atomic structures of a (001)-oriented NiO/(SnO/SnO2) superlattice; Ni atoms are shown in grey, Sn atoms are purple, and O atoms are red. Schematic plots of the band alignment for e, NiO/SnO and f, NiO/SnO2 interface. The bandgap values are obtained according to a bulk calculation with HSE06 functional. g, Energy level diagram for different layers of fabricated devices, including SnO.

Extended Data Fig. 5 Citation for the data used in the manuscript.

a, Fig. 3a; b, Fig. 3b; c, Fig. 4c. The numbers shown in the Figure, refer to the raw number in Extended Data Tables 1 and 2.

Extended Data Fig. 6 Geometrical capacitance effect in photodetectors time response.

Measured fall time of the pixels is plotted vs. pixel area (mm2). The area for direct probe connection is estimated with the extension of the capacitance-limited regime. The area could be smaller than the estimated one. Area effect on response time of silicon photodetector is also compared with PbSn. Silicon below 0.1 mm2 reaches the plateau, and further decrease in the area does not decrease the response time. This behaviour indicates that the relatively poor carrier mobility limits the speed of Si PIN PDs.

Extended Data Fig. 7 Impedance measurement of the PbSn device.

a, Impedance plot measured in the dark under short-circuit conditions. b, Capacitance spectra obtained under the same condition as panel a. Black lines correspond to fits. c, Modified Randles equivalent circuit used for the fitting with Rs, Cg, and Cs related to series resistance, geometrical capacitance, and interface accumulation capacitance and R2 and R1 as surface recombination resistance. d, Parameters obtained by fitting the impedance data with Randles equivalent circuit.

Extended Data Fig. 8 Mapping of the distance using PbSn photodetector.

a, The input for the mirror’s position in the ToF setup shown in Fig. 5a for 105 individual measurements. The motorized stage controls the position of the mirror (distance in respect to the light source). The distance of zero is arbitrary, and it means that light is traveling the same distance as the reference pathway toward the InGaAs detector in the interferometer. b, Graph showing the response when the mirror has moved by 1.0, 3.0, 5.0, and 7.0 mm. For better visualization of peak positions, the response magnitude has multiplied by a power of 400. Averages and standard deviations of estimated depths based on the response time are shown on right side c, The output of the estimated distances using the peak position of PbSn photodetector response. The 3D visualization of these results is shown in Fig. 5d.

Extended Data Table 1 Comparison of the solution-processed photodetectors
Full size table
Extended Data Table 2 Comparison of commercial silicon photodetector
Full size table

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Supplementary Information

Supplementary Notes 1 and 2, Figs. 1–11 and Tables 1–4.

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Morteza Najarian, A., Vafaie, M., Johnston, A. et al. Sub-millimetre light detection and ranging using perovskites. Nat Electron 5, 511–518 (2022). https://doi.org/10.1038/s41928-022-00799-7

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