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Light-activated interlayer contraction in two-dimensional perovskites for high-efficiency solar cells

Nature Nanotechnology volume 17, pages 45–52 (2022)Cite this article

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Abstract

Understanding and tailoring the physical behaviour of halide perovskites under practical environments is critical for designing efficient and durable optoelectronic devices. Here, we report that continuous light illumination leads to >1% contraction in the out-of-plane direction in two-dimensional hybrid perovskites, which is reversible and strongly dependent on the specific superlattice packing. X-ray photoelectron spectroscopy measurements show that constant light illumination results in the accumulation of positive charges in the terminal iodine atoms, thereby enhancing the bonding character of inter-slab I–I interactions across the organic barrier and activating out-of-plane contraction. Correlated charge transport, structural and photovoltaic measurements confirm that the onset of the light-induced contraction is synchronized to a threefold increase in carrier mobility and conductivity, which is consistent with an increase in the electronic band dispersion predicted by first-principles calculations. Flux-dependent space-charge-limited current measurement reveals that light-induced interlayer contraction activates interlayer charge transport. The enhanced charge transport boosts the photovoltaic efficiency of two-dimensional perovskite solar cells up to 18.3% by increasing the device’s fill factor and open-circuit voltage.

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Fig. 1: Evolution of the structure of the DJ n = 3 perovskites under continuous light illumination.
Fig. 2: Mechanistic origin of the light-induced contraction.
Fig. 3: Interlayer distance and band structure.
Fig. 4: Electron mobility as a function of light illumination.
Fig. 5: Effects of continuous light illumination on the performance of 2D perovskite solar cells.

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The data for this study are available from the authors upon reasonable request.

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The analysis code for this study is available from the authors upon reasonable request.

References

  1. Mitzi, D. B., Chondroudis, K. & Kagan, C. R. Organic-inorganic electronics. IBM J. Res. Dev. 45, 29–45 (2001).

    Article  CAS  Google Scholar 

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

    Article  CAS  Google Scholar 

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

    Article  CAS  Google Scholar 

  4. Long, G. et al. Spin control in reduced-dimensional chiral perovskites. Nat. Photon. 12, 528–533 (2018).

    Article  CAS  Google Scholar 

  5. Lu, H. et al. Spin-dependent charge transport through 2D chiral hybrid lead-iodide perovskites. Sci. Adv. 5, eaay0571 (2019).

    Article  CAS  Google Scholar 

  6. Chen, Y. et al. 2D Ruddlesden–Popper perovskites for optoelectronics. Adv. Mater. 30, 1703487 (2018).

    Article  Google Scholar 

  7. Cao, D. H., Stoumpos, C. C., Farha, O. K., Hupp, J. T. & Kanatzidis, M. G. 2D homologous perovskites as light-absorbing materials for solar cell applications. J. Am. Chem. Soc. 137, 7843–7850 (2015).

    Article  CAS  Google Scholar 

  8. Mao, L., Stoumpos, C. C. & Kanatzidis, M. G. Two-dimensional hybrid halide perovskites: principles and promises. J. Am. Chem. Soc. 141, 1171–1190 (2019).

    Article  CAS  Google Scholar 

  9. Billing, D. G. & Lemmerer, A. Synthesis, characterization and phase transitions of the inorganic–organic layered perovskite-type hybrids [(CnH2n+1NH3)2PbI4] (n = 12, 14, 16 and 18). New J. Chem. 32, 1736–1746 (2008).

    Article  CAS  Google Scholar 

  10. Billing, D. G. & Lemmerer, A. Synthesis and crystal structures of inorganic–organic hybrids incorporating an aromatic amine with a chiral functional group. CrystEngComm 8, 686–695 (2006).

    Article  CAS  Google Scholar 

  11. Mitzi, D. B. in Progress in Inorganic Chemistry Vol. 48 (ed. Karlin, K. D.) 1–121 (John Wiley & Sons, 1999).https://doi.org/10.1002/9780470166499.ch1

  12. Tu, Q. et al. Out-of-plane mechanical properties of 2D hybrid organic–inorganic perovskites by nanoindentation. ACS Appl. Mater. Interfaces 10, 22167–22173 (2018).

    Article  CAS  Google Scholar 

  13. Reyes-Martinez, M. A. et al. Unraveling the elastic properties of (quasi) two-dimensional hybrid perovskites: a joint experimental and theoretical study. ACS Appl. Mater. Interfaces 12, 17881–17892 (2020).

    Article  CAS  Google Scholar 

  14. Katan, C., Mercier, N. & Even, J. Quantum and dielectric confinement effects in lower-dimensional hybrid perovskite semiconductors. Chem. Rev. 119, 3140–3192 (2019).

    Article  CAS  Google Scholar 

  15. Spanopoulos, I. et al. Uniaxial expansion of the 2D Ruddlesden–Popper perovskite family for improved environmental stability. J. Am. Chem. Soc. 141, 5518–5534 (2019).

    Article  CAS  Google Scholar 

  16. Gompel, W. T. M. V. et al. Towards 2D layered hybrid perovskites with enhanced functionality: introducing charge-transfer complexes via self-assembly. Chem. Commun. 55, 2481–2484 (2019).

    Article  Google Scholar 

  17. Ahn, J. et al. A new class of chiral semiconductors: chiral-organic-molecule-incorporating organic–inorganic hybrid perovskites. Mater. Horiz. 4, 851–856 (2017).

    Article  CAS  Google Scholar 

  18. Mao, L. et al. Hybrid Dion–Jacobson 2D lead iodide perovskites. J. Am. Chem. Soc. 140, 3775–3783 (2018).

    Article  CAS  Google Scholar 

  19. Soe, C. M. M. et al. New type of 2D perovskites with alternating cations in the interlayer space, (C(NH2)3)(CH3NH3)nPbnI3n+1: structure, properties, and photovoltaic performance. J. Am. Chem. Soc. 139, 16297–16309 (2017).

    Article  CAS  Google Scholar 

  20. Tsai, H. et al. Design principles for electronic charge transport in solution-processed vertically stacked 2D perovskite quantum wells. Nat. Commun. 9, 2130 (2018).

    Article  Google Scholar 

  21. Zhang, Y., Sun, M., Zhou, N., Huang, B. & Zhou, H. Electronic tunability and mobility anisotropy of quasi-2D perovskite single crystals with varied spacer cations. J. Phys. Chem. Lett. 11, 7610–7616 (2020).

    Article  CAS  Google Scholar 

  22. Soe, C. M. M. et al. Structural and thermodynamic limits of layer thickness in 2D halide perovskites. Proc. Natl Acad. Sci. USA 116, 58–66 (2019).

    Article  Google Scholar 

  23. Leng, K. et al. Molecularly thin two-dimensional hybrid perovskites with tunable optoelectronic properties due to reversible surface relaxation. Nat. Mater. 17, 908–914 (2018).

    Article  CAS  Google Scholar 

  24. Liu, G. et al. Isothermal pressure-derived metastable states in 2D hybrid perovskites showing enduring bandgap narrowing. Proc. Natl Acad. Sci. USA 115, 8076–8081 (2018).

    Article  CAS  Google Scholar 

  25. Liu, S. et al. Manipulating efficient light emission in two-dimensional perovskite crystals by pressure-induced anisotropic deformation. Sci. Adv. 5, eaav9445 (2019).

    Article  CAS  Google Scholar 

  26. Yu, S. et al. Nonconfinement structure revealed in Dion–Jacobson type quasi-2D perovskite expedites interlayer charge transport. Small 15, 1905081 (2019).

    Article  CAS  Google Scholar 

  27. Blancon, J.-C., Even, J., Stoumpos, C. C., Kanatzidis, M. G. & Mohite, A. D. Semiconductor physics of organic–inorganic 2D halide perovskites. Nat. Nanotechnol. 15, 969–985 (2020).

    Article  CAS  Google Scholar 

  28. Svensson, P. H. & Kloo, L. Synthesis, structure, and bonding in polyiodide and metal iodide-iodide systems. Chem. Rev. 103, 1649–1684 (2003).

    Article  CAS  Google Scholar 

  29. Giovanni, D. et al. The physics of interlayer exciton delocalization in Ruddlesden–Popper lead halide perovskites. Nano Lett. 21, 405–413 (2021).

    Article  CAS  Google Scholar 

  30. Santomauro, F. G. et al. Localized holes and delocalized electrons in photoexcited inorganic perovskites: watching each atomic actor by picosecond X-ray absorption spectroscopy. Struct. Dyn. 4, 044002 (2016).

    Article  Google Scholar 

  31. Zu, F.-S. et al. Impact of white light illumination on the electronic and chemical structures of mixed halide and single crystal perovskites. Adv. Opt. Mater. 5, 1700139 (2017).

    Article  Google Scholar 

  32. Blancon, J.-C. et al. Extremely efficient internal exciton dissociation through edge states in layered 2D perovskites. Science 355, 1288–1292 (2017).

    Article  CAS  Google Scholar 

  33. Zhang, Z., Fang, W.-H., Tokina, M. V., Long, R. & Prezhdo, O. V. Rapid decoherence suppresses charge recombination in multi-layer 2D halide perovskites: time-domain ab initio analysis. Nano Lett. 18, 2459–2466 (2018).

    Article  CAS  Google Scholar 

  34. Neutzner, S. et al. Exciton-polaron spectral structures in two-dimensional hybrid lead-halide perovskites. Phys. Rev. Mater. 2, 064605 (2018).

    Article  CAS  Google Scholar 

  35. Ren, H. et al. Efficient and stable Ruddlesden–Popper perovskite solar cell with tailored interlayer molecular interaction. Nat. Photon. 14, 154–163 (2020).

    Article  CAS  Google Scholar 

  36. Shi, D. et al. Low trap-state density and long carrier diffusion in organolead trihalide perovskite single crystals. Science 347, 519–522 (2015).

    Article  CAS  Google Scholar 

  37. Goodman, A. M. & Rose, A. Double extraction of uniformly generated electron−hole pairs from insulators with noninjecting contacts. J. Appl. Phys. 42, 2823–2830 (1971).

    Article  CAS  Google Scholar 

  38. Mihailetchi, V. D., Wildeman, J. & Blom, P. W. M. Space-charge limited photocurrent. Phys. Rev. Lett. 94, 126602 (2005).

    Article  CAS  Google Scholar 

  39. 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 

  40. Kirkpatrick, S. Percolation and conduction. Rev. Mod. Phys. 45, 574–588 (1973).

    Article  Google Scholar 

  41. Seager, C. H. & Pike, G. E. Percolation and conductivity: a computer study. II. Phys. Rev. B 10, 1435–1446 (1974).

    Article  CAS  Google Scholar 

  42. Britnell, L. et al. Strong light-matter Interactions in heterostructures of atomically thin films. Science 340, 1311–1314 (2013).

    Article  CAS  Google Scholar 

  43. Xia, F., Wang, H., Xiao, D., Dubey, M. & Ramasubramaniam, A. Two-dimensional material nanophotonics. Nat. Photonics 8, 899–907 (2014).

    Article  CAS  Google Scholar 

  44. Stoumpos, C. et al. Ruddlesden−Popper hybrid lead iodide perovskite 2D homologous semiconductors. Chem. Mater. 28, 2852–2867 (2016).

    Article  CAS  Google Scholar 

  45. He, X. Oriented growth of ultrathin single crystals of 2D Ruddlesden–Popper hybrid lead iodide perovskite for high-performance photodetector. ACS Appl. Mater. Interfaces 11, 15905–15912 (2019).

    Article  CAS  Google Scholar 

  46. Jiang, Z. et al. The dedicated high-resolution grazing-incidence X-ray scattering beamline 8-ID-E at the Advanced Photon Source. J. Synchrotron Radiat. 19, 627–636 (2012).

    Article  CAS  Google Scholar 

  47. Yager, K. G. et al. SciAnalysis. GitHub https://github.com/CFN-softbio/SciAnalysis (2021).

  48. Sanchez-Bajo, R. & Cumbrera, F. L. The use of the Pseudo-Voigt function in variance method of X-ray line-broadening analysis. J. Appl. Crystallogr. 30, 427–430 (1997).

    Article  CAS  Google Scholar 

  49. Patterson, A. L. The Scherrer formula for X-ray particle size determination. Phys. Rev. 56, 978–982 (2019).

    Article  Google Scholar 

  50. Smiligies, D.-M. Scherrer grain-size analysis adapted to grazing incidence scattering with area detectors. J. Appl. Crystallogr. 42, 1030–1034 (2009).

    Article  Google Scholar 

  51. Hohenberg, P. & Kohn, W. Inhomogeneous electron gas. Phys. Rev. 136, B864–B871 (1964).

    Article  Google Scholar 

  52. Kohn, W. & Sham, L. J. Self-consistent equations including exchange and correlation effects. Phys. Rev. 140, A1133–A1138 (1965).

    Article  Google Scholar 

  53. Soler, J. M. et al. The SIESTA method for ab initio order-N materials simulation. J. Phys. Condens. Matter. 14, 2745–2779 (2002).

    Article  CAS  Google Scholar 

  54. Cooper, V. W. Van der Waals density functional: an appropriate exchange functional. Phys. Rev. B 81, 161104 (2010).

    Article  Google Scholar 

  55. Hamada, I. & Otani, M. Comparative van der Waals density functional study of graphene on metal surfaces. Phys. Rev. B 82, 153412 (2010).

    Article  Google Scholar 

  56. Yuk, S. F. et al. Towards an accurate description of perovskite ferroelectrics: exchange and correlations effects. Sci. Rep. 7, 1738 (2017).

    Google Scholar 

  57. Traore, B. et al. Importance of vacancies and doping in hole-transporting nickel oxide interface with halide perovskites. ACS Appl. Mater. Interface 12, 6633–6640 (2020).

    Article  CAS  Google Scholar 

  58. Troullier, N. & Martins, J. L. Efficient pseudopotentials for plane-wave calculations. Phys. Rev. B 43, 1993–2006 (1991).

    Article  CAS  Google Scholar 

  59. Bitzek, E. et al. Structural relaxation made simple. Phys. Rev. Lett. 97, 170201 (2006).

    Article  Google Scholar 

Download references

Acknowledgements

The work at Rice University was supported by the US Department of Defense Short-Term Innovative Research (STIR) programme funded by the Army Research Office. J. Even acknowledges the financial support from the Institut Universitaire de France. W.L. acknowledges the National Science Foundation Graduate Research Fellowship Program. This material is based upon work supported by the National Science Foundation Graduate Research Fellowship Program under grant no. NSF 20-587. Any opinions, findings and conclusions or recommendations expressed in this material are those of the author and do not necessarily reflect the views of the National Science Foundation. Work at Northwestern on the stability of perovskite solar cells was supported by the Office of Naval Research (N00014-20-1-2725). DFT calculations were performed at Institut FOTON as well as Institut des Sciences Chimiques de Rennes, and the work was granted access to the HPC resources of Très Grand Centre de Calcul du CEA (TGCC), the Centre Informatique National de I’Enseignement Supérieur (CINES) and Institut du développement et des ressources en informatique scientifique (IDRIS) under allocations 2019-A0060906724 and 2019-A0070907682 made by Grand Équipement National de Calcul Intensif (GENCI). This research used facilities of the APS, a US Department of Energy Office of Science User Facility operated for the Department of Energy Office of Science by Argonne National Laboratory under contract no. DE−AC02-06CH11357. This research used beamline 11-BM (CMS) of the NSLS-II and the Center for Functional Nanomaterials, both of which are US Department of Energy Office of Science User Facilities operated for the Department of Energy Office of Science by Brookhaven National Laboratory under contract no. DE-SC0012704. We acknowledge the help of B. Chen for supervising the XPS measurements. We thank R. Li for his assistance performing experiments at beamline CMS. The work at Purdue University was supported by the National Science Foundation under grant no. 1724728, CIF21 DIBBs: EI: Creating a Digital Environment for Enabling Data-Driven Science (DEEDS), awarded by the Office of Advanced Cyberinfrastructure.

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Authors and Affiliations

  1. Department of Chemical and Biomolecular Engineering, Rice University, Houston, TX, USA

    Wenbin Li, Siraj Sidhik, Hao Zhang, Austin Fehr, Joseph Essman, Yafei Wang, Jean-Christophe Blancon & Aditya D. Mohite

  2. Applied Physics Program, Smalley-Curl Institute, Rice University, Houston, TX, USA

    Wenbin Li, Hao Zhang & Aditya D. Mohite

  3. Institut FOTON, University Rennes, INSA Rennes, CNRS, Rennes, France

    Siraj Sidhik & Boubacar Traore

  4. Univ Rennes, ENSCR, INSA Rennes, CNRS, ISCR (Institut des Sciences Chimiques de Rennes) -UMR 6226, Rennes, France

    Boubacar Traore & Claudine Katan

  5. School of Electrical and Computer Engineering, Purdue University, West Lafayette, IN, USA

    Reza Asadpour, Muhammad A. Alam & Jacky Even

  6. Department of Materials Science and NanoEngineering, Rice University, Houston, TX, USA

    Jin Hou

  7. Department of Chemistry, Department of Materials Science and Engineering, Northwestern University, Evanston, IL, USA

    Justin M. Hoffman, Ioannis Spanopoulos & Mercouri G. Kanatzidis

  8. Los Alamos National Laboratory, Los Alamos, NM, USA

    Jared J. Crochet

  9. Center for Functional Nanomaterials, Brookhaven National Laboratory, Brookhaven, NY, USA

    Esther Tsai

  10. X-Ray Science Division, Argonne National Laboratory, Argonne, IL, USA

    Joseph Strzalka

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Contributions

A.D.M. and J.-C.B. conceived the concept, designed the experiment and wrote the manuscript. S.S. and J. Hoffman synthesized the perovskite crystals and prepared the samples with the help of J. Hou and W.L., and under the supervision of M.G.K.; S.S. fabricated thin films and the solar cells and performed solar cell characterization. W.L. measured and analysed the GIWAXS patterns with the help of H.Z., Y.W., A.F., J. Essman, J.S. and E.T., and performed indexing with guidance from J. Even and J.-C.B. DFT calculations were performed by B.T. with guidance from J. Even and C.K. Device modelling was done by R.A. and advised by M.A.A. J.J.C. helped with the data analysis. All authors read the manuscript and agree to its contents, and all data are reported in the main text and Supplementary Information.

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Correspondence to Jean-Christophe Blancon or Aditya D. Mohite.

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Supplementary Figs. 1–10, Tables 1–14, Discussion and references.

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Li, W., Sidhik, S., Traore, B. et al. Light-activated interlayer contraction in two-dimensional perovskites for high-efficiency solar cells. Nat. Nanotechnol. 17, 45–52 (2022). https://doi.org/10.1038/s41565-021-01010-2

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