An Experimental and Computational Assessment of Long-chain Sulfonium Capping Ligands for Perovskite Quantum Dots

Oleksandr Kolomiiets^a^,^b, Andriy Stelmakh^a^,^b, Sebastian Sabisch^a^,^b, Amrutha Rajan^a^,^b, Lidiia Dubenska^a^,^b, Andrij Baumketner^c, Gabriele Raino^a^,^b, Maryna Bodnarchuk^a^,^b, Maksym Kovalenko^a^,^b

^aLaboratory of Inorganic Chemistry, Department of Chemistry and Applied Biosciences, ETH Zürich, CH-8093 Zürich, Switzerland

^bLaboratory of Thin Films and Photovoltaics, Empa — Swiss Federal Laboratories for Materials Science and Technology, Ueberlandstrasse, 129, Dübendorf, Switzerland

^cInstitute for Condensed Matter Physics, NAS of Ukraine, Lviv 79011, Ukraine

Proceedings of MATSUS Fall 2024 Conference (MATSUSFall24)

#PeroMAT- Halide perovskite and perovskite- inspired materials: synthesis and applications

Lausanne, Switzerland, 2024 November 12th - 15th

Organizers: Raquel Galian, Lakshminarayana Polavarapu and Paola Vivo

Oral, Oleksandr Kolomiiets, presentation 182
Publication date: 28th August 2024

Lead halide perovskite nanocrystals (LHP NCs) exhibit instability due to the dynamic and labile nature of both their inorganic core and the organic-inorganic interface, adversely impacting their optical and electronic properties [1]. The quest for novel capping ligands has not stopped, rather contrary [2], given the ever-expanding expectations for LHP NCs' deployment as classical and quantum light sources [3, 4]. We hypothesized that the facile molecular engineering of sulfonium salts as X-type ligands could enable highly customized surface chemistries for LHP NCs. Molecular dynamics simulations indicated that sulfonium ligands with diverse tail and headgroup structures exhibit equal or greater affinity to CsPbBr3 surfaces compared to their broadly studied ammonium counterparts. CsPbBr3 NCs capped with sulfonium bromides exhibit photoluminescence quantum yields exceeding 90% in colloids and enhanced durability in the typical purification processes. The compactness of the headgroup and tail branching significantly govern the long-term colloidal stability and resilience towards dilution and concentration. Further molecular engineering of sulfonium ligands allowed venturing into more demanding MAPbBr3 and FAPbBr3 NCs (MA, methylammonium; FA, formamidinium).

References:

[1] Akkerman, Q.A., Rainò, G., Kovalenko, M.V. et al, Genesis, challenges and opportunities for colloidal lead halide perovskite nanocrystals. Nature Materials 2018, 17(5), 394-405.

[2] Morad, V., Stelmakh, A., Svyrydenko, M. et al. Designer phospholipid capping ligands for soft metal halide nanocrystals. Nature 2024, 626, 542–548.

[3] Liu, M., Wan, Q., Wang, H. et al. Suppression of temperature quenching in perovskite nanocrystals for efficient and thermally stable light-emitting diodes. Nat. Photonics 2021, 15, 379–385.

[4] Rainò, G., Becker, M.A., Bodnarchuk, M.I. et al. Superfluorescence from lead halide perovskite quantum dot superlattices. Nature 2018, 563, 671–675.

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