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Efficient vertical charge transport in polycrystalline halide perovskites revealed by four-dimensional tracking of charge carriers

Nature Materials volume 21, pages 1388–1395 (2022)Cite this article

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Abstract

Fast diffusion of charge carriers is crucial for efficient charge collection in perovskite solar cells. While lateral transient photoluminescence microscopies have been popularly used to characterize charge diffusion in perovskites, there exists a discrepancy between low diffusion coefficients measured and near-unity charge collection efficiencies achieved in practical solar cells. Here, we reveal hidden microscopic dynamics in halide perovskites through four-dimensional (directions x, y and z and time t) tracking of charge carriers by characterizing out-of-plane diffusion of charge carriers. By combining this approach with confocal microscopy, we discover a strong local heterogeneity of vertical charge diffusivities in a three-dimensional perovskite film, arising from the difference between intragrain and intergrain diffusion. We visualize that most charge carriers are efficiently transported through the direct intragrain pathways or via indirect detours through nearby areas with fast diffusion. The observed anisotropy and heterogeneity of charge carrier diffusion in perovskites rationalize their high performance as shown in real devices. Our work also foresees that further control of polycrystal growth will enable solar cells with micrometres-thick perovskites to achieve both long optical path length and efficient charge collection simultaneously.

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Fig. 1: Self-filtering effect on the transient PL spectrum of semiconductors.
Fig. 2: Characterization of the out-of-plane charge diffusion across the FAPbI3 perovskite film.
Fig. 3: Local heterogeneity of the vertical diffusivity in FAPbI3 perovskite.
Fig. 4: Four-dimensional (x, y, z, t) tracking of free charge carriers in FAPbI3 perovskite.
Fig. 5: Anisotropic diffusion in a vertically stacked BA2PbI4 2D perovskite.

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Data availability

The data underlying this paper are available at https://doi.org/10.17863/CAM.88680.

References

  1. Herz, L. M. Charge-carrier mobilities in metal halide perovskites: fundamental mechanisms and limits. ACS Energy Lett. 2, 1539–1548 (2017).

    Article  CAS  Google Scholar 

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

    Article  CAS  Google Scholar 

  3. deQuilettes, D. W. et al. Impact of photon recycling, grain boundaries, and nonlinear recombination on energy transport in semiconductors. ACS Photonics 9, 110–122 (2022).

    Article  CAS  Google Scholar 

  4. Baldwin, A. et al. Local energy landscape drives long-range exciton diffusion in two-dimensional halide perovskite semiconductors. J. Phys. Chem. Lett. 12, 4003–4011 (2021).

    Article  CAS  Google Scholar 

  5. Saidaminov, M. I. et al. Multi-cation perovskites prevent carrier reflection from grain surfaces. Nat. Mater. 19, 412–418 (2020).

    Article  CAS  Google Scholar 

  6. Seitz, M. et al. Exciton diffusion in two-dimensional metal-halide perovskites. Nat. Commun. 11, 2035 (2020).

    Article  CAS  Google Scholar 

  7. Stranks, S. D. Multimodal microscopy characterization of halide perovskite semiconductors: revealing a new world (dis)order. Matter 4, 3852–3866 (2021).

    Article  CAS  Google Scholar 

  8. Guo, Z., Manser, J. S., Wan, Y., Kamat, P. V. & Huang, L. Spatial and temporal imaging of long-range charge transport in perovskite thin films by ultrafast microscopy. Nat. Commun. 6, 7471 (2015).

    Article  CAS  Google Scholar 

  9. Guo, Z. et al. Imaging carrier diffusion in perovskites with a diffractive optic-based transient absorption microscope. J. Phys. Chem. C 122, 10650–10656 (2018).

    Article  CAS  Google Scholar 

  10. Stavrakas, C. et al. Visualizing buried local carrier diffusion in halide perovskite crystals via two-photon microscopy. ACS Energy Lett. 5, 117–123 (2020).

    Article  CAS  Google Scholar 

  11. Tian, W. et al. Limiting perovskite solar cell performance by heterogeneous carrier extraction. Angew. Chem. Int. Ed. 55, 13067–13071 (2016).

    Article  CAS  Google Scholar 

  12. de Quilettes, D. W. et al. Impact of microstructure on local carrier lifetime in perovskite solar cells. Science 348, 683–686 (2015).

    Article  Google Scholar 

  13. Cho, C. et al. Effects of photon recycling and scattering in high-performance perovskite solar cells. Sci. Adv. 7, eabj1363 (2021).

    Article  CAS  Google Scholar 

  14. Degani, M. et al. 23.7% efficient inverted perovskite solar cells by dual interfacial modification. Sci. Adv. 7, eabj7930 (2021).

    Article  CAS  Google Scholar 

  15. Staub, F., Anusca, I., Lupascu, D. C., Rau, U. & Kirchartz, T. Effect of reabsorption and photon recycling on photoluminescence spectra and transients in lead-halide perovskite crystals. J. Phys. Mater. 3, 025003 (2020).

    Article  CAS  Google Scholar 

  16. Yamada, T., Yamada, Y., Nakaike, Y., Wakamiya, A. & Kanemitsu, Y. Photon emission and reabsorption processes in CH3NH3PbBr3 single crystals revealed by time-resolved two-photon-excitation photoluminescence microscopy. Phys. Rev. Appl. 7, 014001 (2017).

    Article  Google Scholar 

  17. Cho, C. et al. The role of photon recycling in perovskite light-emitting diodes. Nat. Commun. 11, 611 (2020).

    Article  CAS  Google Scholar 

  18. Li, Z., Chen, Y. & Burda, C. Photoexcited dynamics in metal halide perovskites: from relaxation mechanisms to applications. J. Phys. Chem. C 123, 3255–3269 (2019).

    Article  CAS  Google Scholar 

  19. Sung, J. et al. Long-range ballistic propagation of carriers in methylammonium lead iodide perovskite thin films. Nat. Phys. 16, 171–176 (2020).

    Article  CAS  Google Scholar 

  20. Guo, Z. et al. Long-range hot-carrier transport in hybrid perovskites visualized by ultrafast microscopy. Science 356, 59–62 (2017).

    Article  CAS  Google Scholar 

  21. Zhang, B., Zerubia, J. & Olivo-Marin, J.-C. Gaussian approximations of fluorescence microscope point-spread function models. Appl. Opt. 46, 1819–1829 (2007).

    Article  Google Scholar 

  22. deQuilettes, D. W. et al. Tracking photoexcited carriers in hybrid perovskite semiconductors: trap-dominated spatial heterogeneity and diffusion. ACS Nano 11, 11488–11496 (2017).

    Article  CAS  Google Scholar 

  23. Feldmann, S. et al. Photodoping through local charge carrier accumulation in alloyed hybrid perovskites for highly efficient luminescence. Nat. Photon. 14, 123–128 (2020).

    Article  CAS  Google Scholar 

  24. Frohna, K. et al. Nanoscale chemical heterogeneity dominates the optoelectronic response of alloyed perovskite solar cells. Nat. Nanotechnol. 17, 190–196 (2022).

    Article  CAS  Google Scholar 

  25. deQuilettes, D. W. et al. Photo-induced halide redistribution in organic–inorganic perovskite films. Nat. Commun. 7, 11683 (2016).

    Article  CAS  Google Scholar 

  26. Musiienko, A. et al. Deciphering the effect of traps on electronic charge transport properties of methylammonium lead tribromide perovskite. Sci. Adv. 6, eabb6393 (2020).

    Article  CAS  Google Scholar 

  27. Kang, G. et al. Electron trapping and extraction kinetics on carrier diffusion in metal halide perovskite thin films. J. Mater. Chem. A 7, 25838–25844 (2019).

    Article  CAS  Google Scholar 

  28. Arias, D. H., Moore, D. T., van de Lagemaat, J. & Johnson, J. C. Direct measurements of carrier transport in polycrystalline methylammonium lead iodide perovskite films with transient grating spectroscopy. J. Phys. Chem. Lett. 9, 5710–5717 (2018).

    Article  CAS  Google Scholar 

  29. Yang, M. et al. Do grain boundaries dominate non-radiative recombination in CH3NH3PbI3 perovskite thin films? Phys. Chem. Chem. Phys. 19, 5043–5050 (2017).

    Article  CAS  Google Scholar 

  30. Ma, C., Shen, D., Ng, T.-W., Lo, M.-F. & Lee, C.-S. 2D perovskites with short interlayer distance for high-performance solar cell application. Adv. Mater. 30, 1800710 (2018).

    Article  Google Scholar 

  31. Niu, T., Xue, Q. & Yip, H.-L. Advances in Dion-Jacobson phase two-dimensional metal halide perovskite solar cells. Nanophotonics 10, 2069–2102 (2020).

    Article  Google Scholar 

  32. Magdaleno, A. J. et al. Efficient interlayer exciton transport in two-dimensional metal-halide perovskites. Mater. Horiz. 8, 639–644 (2021).

    Article  CAS  Google Scholar 

  33. Shi, Z., Ni, Z. & Huang, J. Direct observation of fast carriers transport along out-of-plane direction in a Dion–Jacobson layered perovskite. ACS Energy Lett. 7, 984–987 (2022).

    Article  CAS  Google Scholar 

  34. Jang, Y.-W. et al. Intact 2D/3D halide junction perovskite solar cells via solid-phase in-plane growth. Nat. Energy 6, 63–71 (2021).

    Article  CAS  Google Scholar 

  35. Azmi, R. et al. Damp heat–stable perovskite solar cells with tailored-dimensionality 2D/3D heterojunctions. Science 376, 73–77 (2022).

    Article  CAS  Google Scholar 

  36. Tsai, H. et al. High-efficiency two-dimensional Ruddlesden–Popper perovskite solar cells. Nature 536, 312–316 (2016).

    Article  CAS  Google Scholar 

  37. Ren, Z. et al. High-performance blue perovskite light-emitting diodes enabled by efficient energy transfer between coupled quasi-2D perovskite layers. Adv. Mater. 33, 2005570 (2021).

    Article  CAS  Google Scholar 

  38. Qin, C. et al. Stable room-temperature continuous-wave lasing in quasi-2D perovskite films. Nature 585, 53–57 (2020).

    Article  CAS  Google Scholar 

  39. Chen, J. et al. High-performance thickness insensitive perovskite solar cells with enhanced moisture stability. Adv. Energy Mater. 8, 1800438 (2018).

    Article  Google Scholar 

  40. Momblona, C. et al. Efficient methylammonium lead iodide perovskite solar cells with active layers from 300 to 900 nm. APL Mater. 2, 081504 (2014).

    Article  Google Scholar 

  41. Polman, A., Knight, M., Garnett, E. C., Ehrler, B. & Sinke, W. C. Photovoltaic materials: present efficiencies and future challenges. Science 352, aad4424 (2016).

    Article  Google Scholar 

  42. Mu, C., Pan, J., Feng, S., Li, Q. & Xu, D. Quantitative doping of chlorine in formamidinium lead trihalide (FAPbI3−xClx) for planar heterojunction perovskite solar cells. Adv. Energy Mater. 7, 1601297 (2017).

    Article  Google Scholar 

  43. Jeon, N. J. et al. A fluorene-terminated hole-transporting material for highly efficient and stable perovskite solar cells. Nat. Energy 3, 682–689 (2018).

    Article  CAS  Google Scholar 

  44. Richter, J. M. et al. Enhancing photoluminescence yields in lead halide perovskites by photon recycling and light out-coupling. Nat. Commun. 7, 13941 (2016).

    Article  CAS  Google Scholar 

  45. Cho, C. & Greenham, N. C. Computational study of dipole radiation in re-absorbing perovskite semiconductors for optoelectronics. Adv. Sci. 8, 2003559 (2021).

    Article  CAS  Google Scholar 

  46. Huang, J., Chang, E. & Wu, Y. Optimization of MAPbI3-based perovskite solar cell with textured surface. IEEE J. Photovolt. 9, 1686–1692 (2019).

    Article  Google Scholar 

  47. Selberherr, S. Analysis and Simulation of Semiconductor Devices (Springer Vienna, 1984).

  48. Huang, J.-Y. et al. Influences of dielectric constant and scan rate on hysteresis effect in perovskite solar cell with simulation and experimental analyses. Sci. Rep. 12, 7927 (2022).

    Article  CAS  Google Scholar 

Download references

Acknowledgements

This work was supported by the Engineering and Physical Sciences Research Council (EPSRC) (EP/S030638/1). S.D.S. acknowledges the Royal Society and Tata Group (UF150033), the EPSRC (EP/R023980/1 and EP/M006360/1) and the European Research Council under the European Union’s Horizon 2020 research and innovation programme (HYPERION, grant agreement no. 756962; SOLARX, grant agreement no. 758826). S.F. acknowledges an EPSRC Doctoral Prize Fellowship and is grateful for support from the Winton Programme for the Physics of Sustainability. K.M.Y., M.N.T.K. and J.H.N. acknowledge the National Research Foundation of Korea (NRF) grant funded by the Korean government (Ministry of Science, ICT and Future Planning (MSIP); NRF-2020R1A2C3009115). J.-Y.H. and Y.-R.W. acknowledge the Ministry of Science and Technology (MOST) of Taiwan under grant nos 109-2221-E-002-196-MY2 and MOST 111-2923-E-002-009. T.C.-J.Y. acknowledges the support of a Marie Skłodowska-Curie Individual Fellowship from the European Union’s Horizon 2020 research and innovation programme (PeTSoC, grant agreement no. 891205). J.-Y.H. acknowledges support from the Simons Foundation (grant no. 601946).

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Authors and Affiliations

  1. Cavendish Laboratory, Department of Physics, University of Cambridge, Cambridge, UK

    Changsoon Cho, Sascha Feldmann, Simon Kahmann, Jun-Yu Huang, Terry Chien‐Jen Yang, Samuel D. Stranks & Neil C. Greenham

  2. Rowland Institute, Harvard University, Cambridge, MA, USA

    Sascha Feldmann

  3. School of Civil, Environmental and Architectural Engineering, Korea University, Seoul, Republic of Korea

    Kyung Mun Yeom, Mohammed Nabaz Taher Khayyat & Jun Hong Noh

  4. Global Frontier Center for Multiscale Energy Systems, Seoul National University, Seoul, Republic of Korea

    Yeoun-Woo Jang & Mansoo Choi

  5. Department of Mechanical Engineering, Seoul National University, Seoul, Republic of Korea

    Yeoun-Woo Jang & Mansoo Choi

  6. Department of Chemical Engineering and Biotechnology, University of Cambridge, Cambridge, UK

    Simon Kahmann, Terry Chien‐Jen Yang & Samuel D. Stranks

  7. Graduate Institute of Photonics and Optoelectronics and Department of Electrical Engineering, National Taiwan University, Taipei, Taiwan

    Jun-Yu Huang & Yuh-Renn Wu

  8. Graduate School of Energy and Environment (KU-KIST Green School), Korea University, Seoul, Republic of Korea

    Jun Hong Noh

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Contributions

C.C. and N.C.G. conceived the idea. C.C. performed the confocal TCSPC with the help of S.K. and S.D.S.; C.C. developed the analysis method and performed the diffusion and ray-optics models. S.F. set up and performed the broadband time-resolved PL (intensified charge-coupled device) characterization. K.M.Y. prepared the spin-coated 3D perovskite films and took their SEM images under the supervision of J.H.N.; Y.-W.J. optimized the 2D perovskite films and took their X-ray diffraction patterns under the supervision of M.C.; C.C. measured the UV–visible transmission. K.M.Y. and M.N.T.K. fabricated and characterized the device under the supervision of J.H.N.; J.-Y.H. performed the drift-diffusion model for full devices under the supervision of Y.-R.W.; T.C.-J.Y. prepared the vapour-deposited 3D perovskite films under the supervision of S.D.S.; and S.D.S. and N.C.G. supervised the work. All authors discussed the data and contributed to the manuscript.

Corresponding author

Correspondence to Neil C. Greenham.

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Competing interests

N.C.G. is a cofounder of a company commercializing perovskite emitters. S.D.S. is a cofounder of Swift Solar. The remaining authors declare no competing interests.

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Nature Materials thanks Anton Malko and the other, anonymous, reviewer(s) for their contribution to the peer review of this work.

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Supplementary Figs. 1–15, Notes 1 and 2 and references.

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Cho, C., Feldmann, S., Yeom, K.M. et al. Efficient vertical charge transport in polycrystalline halide perovskites revealed by four-dimensional tracking of charge carriers. Nat. Mater. 21, 1388–1395 (2022). https://doi.org/10.1038/s41563-022-01395-y

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