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Solution-processable mixed-anion cluster chalcohalide Rb6Re6S8I8 in a light-emitting diode

Nature Materials volume 23, pages 230–236 (2024)Cite this article

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Abstract

Rhenium chalcohalide cluster compounds are a photoluminescent family of mixed-anion chalcohalide cluster materials. Here we report the new material Rb6Re6S8I8, which crystallizes in the cubic space group Fm\(\bar{3}\)m and contains isolated [Re6S8I6]4− clusters. Rb6Re6S8I8 has a band gap of 2.06(5) eV and an ionization energy of 5.51(3) eV, and exhibits broad photoluminescence (PL) ranging from 1.01 eV to 2.12 eV. The room-temperature PL exhibits a PL quantum yield of 42.7% and a PL lifetime of 77 μs (99 μs at 77 K). Rb6Re6S8I8 is found to be soluble in multiple polar solvents including N,N-dimethylformamide, which enables solution processing of the material into films with thickness under 150 nm. Light-emitting diodes based on films of Rb6Re6S8I8 were fabricated, demonstrating the potential for this family of materials in optoelectronic devices.

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Fig. 1: Rb6Re6S8I8 crystal structure.
Fig. 2: Rb6Re6S8I8 optical properties.
Fig. 3: Rb6Re6S8I8 thin films.
Fig. 4: Initial Rb6Re6S8I8 LED performance.
Fig. 5: Optimized Rb6Re6S8I8 LED performance.

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Data availability

All data supporting the findings are provided as figures and accompanying tables in the article and Supplementary Information. The X-ray crystallographic coordinates for the structure reported in this study have been deposited at the Cambridge Crystallographic Data Centre (CCDC) with deposit number 2241320. These data can be obtained free of charge from the CCDC via www.ccdc.cam.ac.uk/data_request/cif. Data files for all figures are available from the corresponding author upon reasonable request.

Code availability

The custom codes used in this work are available upon reasonable request.

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Acknowledgements

This work is supported in part by the National Science Foundation through the MRSEC program (NSF-DMR 1720139) at the Materials Research Center and in part through DMR-2305731. The work made use of the IMSERC Physical Characterization facility at Northwestern University, which has received support from the Soft and Hybrid Nanotechnology Experimental (SHyNE) Resource (NSF ECCS-2025633) and from Northwestern University. It also made use of the EPIC and Keck-II facilities of Northwestern University’s NUANCE Center, which have both received support from the SHyNE Resource (NSF ECCS-2025633), the IIN and Northwestern’s MRSEC programme (NSF DMR-1720139). The work made use of the GIANTFab core facility at Northwestern University. GIANTFab is supported by the Institute for Sustainability and Energy at Northwestern and the Office of the Vice President for Research at Northwestern. Photoemission yield spectroscopy in air measurements were carried out with equipment acquired using ONR grant N00014-18-1-2102. This research used resources of the Advanced Photon Source Beamline 8-ID-E, a US Department of Energy (DOE) Office of Science User Facility operated for the DOE Office of Science by Argonne National Laboratory under contract DE-AC02-06CH113. We acknowledge M. Quintero, D. Chica and R. McClain for productive conversations.

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Author notes

  1. Justin M. Hoffman

    Present address: X-Ray Science Division, Argonne National Laboratory, Lemont, IL, USA

Authors and Affiliations

  1. Department of Chemistry, Northwestern University, Evanston, IL, USA

    Craig C. Laing, Daehan Kim, Ido Hadar, Justin M. Hoffman & Mercouri G. Kanatzidis

  2. Department of Materials Science and Engineering, Korea Advanced Institute of Science and Technology, Daejeon, Republic of Korea

    Jinu Park & Byungha Shin

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

    Jiahong Shen, Jiangang He & Chris Wolverton

  4. Materials Science Division, Argonne National Laboratory, Lemont, IL, USA

    Mercouri G. Kanatzidis

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Contributions

C.C.L. developed the concept, performed all material synthesis, performed and analysed X-ray crystallography and characterization measurements, and fabricated both thin films and LED devices in addition to their characterization. D.K., J.P. and B.S. fabricated and characterized thin films and LED devices. J.S., J.H. and C.W. performed theoretical and computational work and identified Raman stretching modes. I.H. carried out low-temperature PL measurements and analysis. J.M.H. carried out grazing-incidence wide-angle scattering measurements and assisted in some thin-film and LED device fabrication. C.C.L. and M.G.K. were the primary writers of the paper and the principal investigators. All authors discussed the results and provided feedback on the paper.

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Correspondence to Mercouri G. Kanatzidis.

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The authors declare the patent application PCT/US2023/028799.

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Nature Materials thanks Hiroshi Kageyama, Mahesh P. Suryawanshi and the other, anonymous, reviewer(s) for their contribution to the peer review of this work.

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Supplementary information

Supplementary Information

Supplementary Figs. 1–24, Tables 1–6 and additional experimental details, crystallographic tables, solubility table, differential thermal analysis, scanning electron microscopy and energy-dispersive spectroscopy, electronic band structure, phonon dispersion, Raman spectra and vibrational stretches, PXRD, film characterization and grazing-incidence wide-angle scattering measurements, and images of material.

Supplementary Data 1

Crystallographic data.

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Laing, C.C., Kim, D., Park, J. et al. Solution-processable mixed-anion cluster chalcohalide Rb6Re6S8I8 in a light-emitting diode. Nat. Mater. 23, 230–236 (2024). https://doi.org/10.1038/s41563-023-01740-9

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