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Compositional and orientational control in metal halide perovskites of reduced dimensionality

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Abstract

Reduced-dimensional metal halide perovskites (RDPs) have attracted significant attention in recent years due to their promising light harvesting and emissive properties. We sought to increase the systematic understanding of how RDPs are formed. Here we report that layered intermediate complexes formed with the solvent provide a scaffold that facilitates the nucleation and growth of RDPs during annealing, as observed via in situ X-ray scattering. Transient absorption spectroscopy of RDP single crystals and films enables the identification of the distribution of quantum well thicknesses. These insights allow us to develop a kinetic model of RDP formation that accounts for the experimentally observed size distribution of wells. RDPs exhibit a thickness distribution (with sizes that extend above n = 5) determined largely by the stoichiometric proportion between the intercalating cation and solvent complexes. The results indicate a means to control the distribution, composition and orientation of RDPs via the selection of the intercalating cation, the solvent and the deposition technique.

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Fig. 1: Structure and diffraction of RDPs.
Fig. 2: Ultrafast TA spectra of RDPs.
Fig. 3: Formation kinetics of RDPs via in situ GIWAXS.
Fig. 4: Statistical model of the formation of RDPs.
Fig. 5: Orientational analysis of RDPs.

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Data availability

The data that support the plots within this paper are available from the corresponding author upon request.

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Acknowledgements

This article is based in part on work supported by the Ontario Research Fund Research Excellence Program, by the Natural Sciences and Engineering Research Council (NSERC) of Canada, by the US Department of the Navy, Office of Naval Research (grant no. N00014-17-1-2524) and by the King Abdullah University of Science and Technology (KAUST) award no. KUS-11-009-21. Use of the Stanford Synchrotron Radiation Lightsource, SLAC National Accelerator Laboratory, is supported by the US Department of Energy, Office of Science, Office of Basic Energy Sciences, under contract no. DE-AC02-76SF00515. A.G. is supported by NSF GRFP (DGE-1147470). CHESS is supported by the NSF and NIH/NIGMS via NSF award DMR-1332208. We acknowledge D.-M. Smilgies for assistance with GISAXS measurements and E. Dauzon for assistance with spinning in situ GIWAXS measurements at the D-line at CHESS. Some of the synchrotron measurements were performed at the HXMA beamline in the CLS, which is funded by the Canada Foundation for Innovation, the NSERC, the Canadian Institutes of Health Research, the Government of Saskatchewan, Western Economic Diversification Canada and the University of Saskatchewan. Measurements were also conducted at the NSRRC in Hsinchu, Taiwan. The authors acknowledge the technical assistance and scientific guidance of C. Y. Kim at the CLS, and U.-S. Jeong at the NSRRC. The authors thank G. Walters, O. Ouellette, L. N. Quan and H. Tan for fruitful discussions.

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Authors and Affiliations

  1. Department of Electrical and Computer Engineering, University of Toronto, Toronto, Ontario, Canada

    Rafael Quintero-Bermudez, Andrew H. Proppe, Zhenyu Yang & Edward H. Sargent

  2. SLAC National Accelerator Laboratory, Menlo Park, CA, USA

    Aryeh Gold-Parker & Michael F. Toney

  3. Stanford University Department of Chemistry, Stanford, CA, USA

    Aryeh Gold-Parker

  4. Department of Chemistry, University of Toronto, Toronto, Ontario, Canada

    Andrew H. Proppe & Shana O. Kelley

  5. King Abdullah University of Science and Technology (KAUST), KAUST Solar Center (KSC), and Physical Sciences and Engineering Division, Thuwal, Saudi Arabia

    Rahim Munir & Aram Amassian

  6. Department of Pharmaceutical Sciences, Leslie Dan Faculty of Pharmacy, University of Toronto, Toronto, Ontario, Canada

    Shana O. Kelley

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  1. Rafael Quintero-Bermudez
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Contributions

R.Q.-B. and E.H.S. designed and directed this study. R.Q.-B. prepared the samples. R.Q.-B., A.G.-P., R.M. and Z.Y. carried out the synchrotron X-ray scattering experiments. R.Q.-B. and A.G.-P. performed the analysis of the X-ray scattering data, supported and advised by M.F.T. R.Q.-B. carried out the TA spectroscopy measurements and both R.Q.-B. and A.H.P. performed the analysis of this data. R.Q.-B. and A.H.P. fabricated and tested the solar cells. S.O.K., A.A., M.F.T. and E.H.S. supervised the work. R.Q.-B., A.G.-P., M.F.T. and E.H.S. wrote the manuscript with critical input from all the authors.

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Correspondence to Edward H. Sargent.

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Supplementary information

Supplementary information

Supplementary Figures 1–32, Supplementary Tables 1–2, Supplementary References 1–18

Reporting Summary

Supplementary Video 1

Growth of 〈n〉 = 5 in DMF. Video depicting the evolution of the GIWAXS patterns over the course of the annealing process (analysed in Fig. 3) for the following sample: growth of 〈n〉 = 5 in DMF

Supplementary Video 2

Growth of 〈n〉 = 5 in NMP. Video depicting the evolution of the GIWAXS patterns over the course of the annealing process (analysed in Fig. 3) for the following sample: growth of 〈n〉 = 5 in NMP

Supplementary Video 3

Growth of 〈n〉 = 5 in DMSO. Video depicting the evolution of the GIWAXS patterns over the course of the annealing process (analysed in Fig. 3) for the following sample: growth of 〈n〉 = 5 in DMSO

Supplementary Video 4

Growth of 〈n〉 = 10 in DMSO. Video depicting the evolution of the GIWAXS patterns over the course of the annealing process (analysed in Fig. 3) for the following sample: growth of 〈n〉 = 10 in DMSO

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Quintero-Bermudez, R., Gold-Parker, A., Proppe, A.H. et al. Compositional and orientational control in metal halide perovskites of reduced dimensionality. Nature Mater 17, 900–907 (2018). https://doi.org/10.1038/s41563-018-0154-x

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