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Synthesis of 2D perovskite crystals via progressive transformation of quantum well thickness

Nature Synthesis volume 3, pages 265–275 (2024)Cite this article

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Abstract

Two-dimensional (2D) multilayered halide perovskites have emerged as a platform for understanding organic–inorganic interactions, tuning quantum confinement effects and realizing efficient and durable optoelectronic devices. However, reproducibly synthesizing 2D perovskite crystals with a perovskite-layer thickness (quantum well thickness, n-value) >2 using existing crystal growth methods is challenging. Here we demonstrate a synthetic method, termed kinetically controlled space confinement, for the growth of phase-pure Ruddlesden–Popper and Dion–Jacobson 2D perovskites. Phase-pure growth is achieved by progressively increasing the temperature (for a fixed time) or the crystallization time (at a fixed temperature), which allows for control of the crystallization kinetics. In situ photoluminescence spectroscopy and imaging suggest that the controlled increase in n-value (from lower to higher values of n = 4, 5 and 6) occurs due to intercalation of excess precursor ions. Based on 250 experimental data sets, phase diagrams for both Ruddlesden–Popper and Dion–Jacobson perovskites have been constructed to predict the growth of 2D phases with specific n-values, facilitating the production of 2D perovskite crystals with desired layer thickness.

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Fig. 1: Transformation of 2D RP (n = 3) perovskite using the KCSC method.
Fig. 2: Refined phase diagram of the n-purity of 2D perovskite with temperature and time using the KCSC method.
Fig. 3: Mechanism of transformation of 2D RP (n = 3) perovskite by the KCSC method.
Fig. 4: Temperature and time dependence of quantum-well thickness (n) of 2D perovskites in batch-scale classical synthesis.
Fig. 5: Synthesis capability of transformation-based KCSC.

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Data availability

Crystallographic data for the structures reported in this article have been deposited at the Cambridge Crystallographic Data Centre, under deposition numbers CCDC 2279001 (DJ n = 5) and 2279002 (DJ n = 6). All of the data supporting the findings of this study are available in the Article and its Supplementary Information.

Code availability

The analysis code for this study is available at https://github.com/lwb56/KCSC_2D_perovskite

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Acknowledgements

A.D.M. acknowledges support from the Army Research Office (grant W911NF2210158). J.H. acknowledges financial support from the China Scholarships Council (number 202107990007). 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 number 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 University on perovskite solar cells is supported by the Office of Naval Research (grant N00014-20-1-2725). This work made use of the IMSERC crystallography facility at Northwestern University, which has received support from the Soft and Hybrid Nanotechnology Experimental (SHyNE) Resource (NSF ECCS-2025633) and from Northwestern University. Purchase of the silver-microsource diffractometer used to obtain results included in this publication was supported by the Major Research Instrumentation Program from the National Science Foundation under the award CHE-1920248. D.J. acknowledges primary support for this work by the US Army Research Office under contract number W911NF-19-1-0109 and the Sloan Fellowship in Chemistry awarded by the Alfred P. Sloan Foundation. S.B.A. gratefully acknowledges the funding received from the Swiss National Science Foundation under the Early Postdoc Mobility grant (P2ELP2_187977) for this work. J.E. acknowledges financial support from the Institut Universitaire de France. The work at ISCR and Institut FOTON was performed with funding from the European Union’s Horizon 2020 research and innovation programme under grant agreement number 861985 (PeroCUBE). 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 number DE-SC0012704. We thank R. Li and E. Tsai for their assistance in performing experiments at beamline CMS. J.H. acknowledges discussions with M. Tang at Rice University and D. Mitzi at Duke University.

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Authors and Affiliations

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

    Jin Hou, Siraj Sidhik, Isaac Metcalf, Xinting Shuai & Aditya D. Mohite

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

    Wenbin Li, Hao Zhang, Anamika Mishra, Jean-Christophe Blancon & Aditya D. Mohite

  3. Applied Physics Graduate Program, Smalley‐Curl Institute, Rice University, Houston, TX, USA

    Wenbin Li & Hao Zhang

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

    Jared Fletcher & Mercouri G. Kanatzidis

  5. Department of Electrical and Systems Engineering, University of Pennsylvania, Philadelphia, PA, USA

    Surendra B. Anantharaman & Deep Jariwala

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

    Claudine Katan

  7. Univ Rennes, INSA Rennes, CNRS, Institut FOTON – UMR 6082, Rennes, France

    Jacky Even

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Contributions

A.D.M., J.-C.B. and J.H. conceived and designed the experiment. J.H. synthesized the perovskite single crystals with the help of S.S. J.H. performed 1D-XRD measurements with the help of I.M., X.S. and A.M. J.H. and H.Z. performed optical characterizations with the help of W.L. and S.B.A. J.H. performed the transformation experiment. W.L. performed the machine learning analysis. J.F. performed the single-crystal X-ray diffraction and refinement of the crystal structure. J.H. performed data analysis with guidance from C.K., D.J., J.-C.B., M.G.K., J.E. and A.D.M. J.H. and W.L. wrote the paper with input from all the other authors. All authors read the paper and agree to its contents.

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Correspondence to Aditya D. Mohite.

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Nature Synthesis thanks Kian Ping Loh and the other, anonymous, reviewer(s) for their contribution to the peer review of this work. Alexandra Groves, in collaboration with the Nature Synthesis team.

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Supplementary information

Supplementary Information

Supplementary discussions 1.1–1.3, Figs. 1–14, Tables 1–16 and references.

Supplementary Data 1

Crystallographic data of DJ n = 5.

Supplementary Data 2

Crystallographic data of DJ n = 6.

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Source Data Fig. 2

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Source Data Fig. 3

Statistical source data

Source Data Fig. 4

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Source Data Fig. 5

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Hou, J., Li, W., Zhang, H. et al. Synthesis of 2D perovskite crystals via progressive transformation of quantum well thickness. Nat. Synth 3, 265–275 (2024). https://doi.org/10.1038/s44160-023-00422-3

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