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PreprintCC BYChemRxiv

Site-selective alkali ion alloying in double perovskites via liquid-assisted mechanosynthesis revealed by solid-state NMR

  • Kaja Glazer1,2
  • Julia Wiktor3,4
  • Luis Simbari1,2
  • Mo Al Al Maoued5,6
  • Anya Fairhurst1,2
  • Amita Ummadishingu5,6
  • Dominik J. Kubicki1,2
  • Benjamin M. Gallant1,2,7
7 affiliations
  1. 1School of Chemistry
  2. 2University of Birmingham
  3. 3Department of Physics and Astronomy
  4. 4Chalmers University of Technology
  5. 5Department of Chemical Engineering
  6. 6University College London
  7. 7Department of Solution-Processing of Hybrid Materials and Devices Helmholtz-Zentrum Berlin für Materialien und Energie GmbH, Kekuléstraße 5, Berlin, Germany, 12489
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Abstract

Lead-free halide double perovskites are promising materials for light-emitting and photovoltaic applications. However, compositional tuning of their structural and optoelectronic properties has largely focused on B-site and halide alloying. In this work, we show that Cs + on the perovskite A-site of Cs 2 AgInCl 6 can be partly substituted with Rb + using simple apolar liquid-assisted mechanochemistry. By comparing Rb + with Na + substitution we show that ion size drives the site-selectivity of alkali ion substitution into double perovskites, with Na + preferentially occupying the perovskite B-site. By combining multinuclear solid-state nuclear magnetic resonance spectroscopy with X-ray diffraction, we show that Rb+ not only enters the double-perovskite site-selectively but also induces local symmetry breaking of the cubic structure, comparable to the effect of B-site Na + /Ag + alloying, with important implications for symmetry-forbidden photoluminescence emissivity. This work extends the tuneable compositional range of lead-free double perovskites to include A-site mixing while also establishing the site-selectivity of alkali ion speciation into the double perovskite structure.

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Cite

BibTeXRIS
BibTeX
@misc{glazer2026siteselective,
  title = {{Site-selective alkali ion alloying in double perovskites via liquid-assisted mechanosynthesis revealed by solid-state NMR}},
  author = {Kaja Glazer and Julia Wiktor and Luis Simbari and Mo Al Al Maoued and Anya Fairhurst and Amita Ummadishingu and Dominik J. Kubicki and Benjamin M. Gallant},
  howpublished = {ChemRxiv},
  year = {2026},
  month = aug,
  doi = {10.26434/chemrxiv.15008057/v1},
  url = {https://chemrxiv.org/doi/full/10.26434/chemrxiv.15008057/v1},
  note = {CC BY},
}
RIS
TY  - UNPB
TI  - Site-selective alkali ion alloying in double perovskites via liquid-assisted mechanosynthesis revealed by solid-state NMR
AU  - Kaja Glazer
AU  - Julia Wiktor
AU  - Luis Simbari
AU  - Mo Al Al Maoued
AU  - Anya Fairhurst
AU  - Amita Ummadishingu
AU  - Dominik J. Kubicki
AU  - Benjamin M. Gallant
PY  - 2026
DA  - 2026/08/30
PB  - ChemRxiv
DO  - 10.26434/chemrxiv.15008057/v1
UR  - https://chemrxiv.org/doi/full/10.26434/chemrxiv.15008057/v1
AB  - Lead-free halide double perovskites are promising materials for light-emitting and photovoltaic applications. However, compositional tuning of their structural and optoelectronic properties has largely focused on B-site and halide alloying. In this work, we show that Cs + on the perovskite A-site of Cs 2 AgInCl 6 can be partly substituted with Rb + using simple apolar liquid-assisted mechanochemistry. By comparing Rb + with Na + substitution we show that ion size drives the site-selectivity of alkali ion substitution into double perovskites, with Na + preferentially occupying the perovskite B-site. By combining multinuclear solid-state nuclear magnetic resonance spectroscopy with X-ray diffraction, we show that Rb+ not only enters the double-perovskite site-selectively but also induces local symmetry breaking of the cubic structure, comparable to the effect of B-site Na + /Ag + alloying, with important implications for symmetry-forbidden photoluminescence emissivity. This work extends the tuneable compositional range of lead-free double perovskites to include A-site mixing while also establishing the site-selectivity of alkali ion speciation into the double perovskite structure.
ER  -