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High-entropy halide perovskite single crystals stabilized by mild chemistry

Nature volume 621, pages 282–288 (2023)Cite this article

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Abstract

Although high-entropy materials are excellent candidates for a range of functional materials, their formation traditionally requires high-temperature synthetic procedures of over 1,000 °C and complex processing techniques such as hot rolling1,2,3,4,5. One route to address the extreme synthetic requirements for high-entropy materials should involve the design of crystal structures with ionic bonding networks and low cohesive energies. Here we develop room-temperature-solution (20 °C) and low-temperature-solution (80 °C) synthesis procedures for a new class of metal halide perovskite high-entropy semiconductor (HES) single crystals. Due to the soft, ionic lattice nature of metal halide perovskites, these HES single crystals are designed on the cubic Cs2MCl6 (M=Zr4+, Sn4+, Te4+, Hf4+, Re4+, Os4+, Ir4+ or Pt4+) vacancy-ordered double-perovskite structure from the self-assembly of stabilized complexes in multi-element inks, namely free Cs+ cations and five or six different isolated [MCl6]2– anionic octahedral molecules well-mixed in strong hydrochloric acid. The resulting single-phase single crystals span two HES families of five and six elements occupying the M-site as a random alloy in near-equimolar ratios, with the overall Cs2MCl6 crystal structure and stoichiometry maintained. The incorporation of various [MCl6]2– octahedral molecular orbitals disordered across high-entropy five- and six-element Cs2MCl6 single crystals produces complex vibrational and electronic structures with energy transfer interactions between the confined exciton states of the five or six different isolated octahedral molecules.

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Fig. 1: Synthetic design of high-entropy five- and six-element Cs2MX6 single crystals.
Fig. 2: Phase identification of five- and six-element high-entropy perovskite single crystals.
Fig. 3: Elemental analysis of high-entropy perovskite single crystals to confirm incorporation of five or six elements on the M-site.
Fig. 4: Highly resolved structural determination of the absolute configuration of M-site metal centres in high-entropy perovskite single crystals.
Fig. 5: Confirmation of the disordered nature of the five or six different [MCl6]2– octahedral complexes throughout single-phase, high-entropy perovskite systems with no microstructural grain formation.
Fig. 6: Optoelectronic behaviour of high-entropy perovskite single crystals.

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Data availability

The data supporting the findings of this study are available within the article and its Supplementary Information, and are available from the corresponding author on reasonable request. The crystallographic information files have also been deposited in the Inorganic Crystal Structure Database under reference nos. CSD 2216614–2216620, 2216624, 2216626, 2216627 and 2216636–2216643. These data can be obtained free of charge via https://www.ccdc.cam.ac.uk/structures/, or by emailing data_request@ccdc.cam.ac.uk.

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Acknowledgements

This work was primarily supported by the US Department of Energy, Office of Science, Office of Basic Energy Sciences, Materials Sciences and Engineering Division, under contract no. DE-AC02-05CH11231 within the Fundamentals of Semiconductor Nanowire Program (KCPY23). The authors thank N. S. Settineri at UC Berkeley and S. J. Teat at the Advanced Light Source for their assistance in SCXRD and SCXRD–MAD measurements; A. J. Gubser for helpful discussions in regard to SEM–BSE imaging and EBSD measurements; and J. Grimsich for providing access to the various optical microscopes in the Earth and Planetary Sciences Petrographic Microscope Resource Center. Single-crystal X-ray diffraction studies were performed at the UC Berkeley College of Chemistry Small Molecule X-ray Crystallography Facility and at beamline 12.2.1 of the Advanced Light Source, a US DOE Office of Science User Facility at Lawrence Berkeley National Laboratory under contract no. DE-AC02-05CH11231. Ultra-low-frequency Raman spectroscopy was performed at the Stanford Nano Shared Facilities, supported by the National Science Foundation under award no. ECCS-2026822. M.C.F. acknowledges support from the Kavli ENSI Philomathia Graduate Student Fellowship. J.J. acknowledges fellowship support from Suzhou Industrial Park.

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Author notes

  1. These authors contributed equally: Maria C. Folgueras, Yuxin Jiang

Authors and Affiliations

  1. Department of Materials Science and Engineering, University of California, Berkeley, Berkeley, CA, USA

    Maria C. Folgueras & Peidong Yang

  2. Materials Sciences Division, Lawrence Berkeley National Laboratory, Berkeley, CA, USA

    Maria C. Folgueras, Yuxin Jiang & Peidong Yang

  3. Kavli Energy NanoScience Institute, Berkeley, CA, USA

    Maria C. Folgueras & Peidong Yang

  4. Department of Chemistry, University of California, Berkeley, Berkeley, CA, USA

    Yuxin Jiang, Jianbo Jin & Peidong Yang

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Contributions

M.C.F. and P.Y. conceived the idea. M.C.F., Y.J. and P.Y. designed the research. M.C.F. and Y.J. led the study and conducted materials synthesis, major characterization and data analysis including PXRD, SCXRD, SEM imaging, SEM–EDX, SEM–EBSD, ICP–AES, Raman, UV-visible absorption, photoluminescence and theoretical calculations. Y.J. and J.J. conducted SCXRD–MAD experiments. M.C.F. conducted X-ray fluorescence analysis. J.J. analysed SCXRD–MAD datasets. M.C.F., Y.J. and P.Y. wrote the manuscript. All authors discussed the results and revised the manuscript.

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Correspondence to Peidong Yang.

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Folgueras, M.C., Jiang, Y., Jin, J. et al. High-entropy halide perovskite single crystals stabilized by mild chemistry. Nature 621, 282–288 (2023). https://doi.org/10.1038/s41586-023-06396-8

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