Structurally Tailored Zwitterionic Phospholipid Capping Ligands for Lead Halide Perovskite Nanocrystals

Viktoriia Morad^a^,^b, Andriy Stelmakh^a^,^b, Mariia Svyrydenko^a^,^b, Leon Feld^a^,^b, Marcel Aebli^a^,^b, Andrij Baumketner^c, 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, Dübendorf, Switzerland, Ueberlandstrasse, 129, Dübendorf, Switzerland

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

Proceedings of International Conference on Emerging Light Emitting Materials (EMLEM22)

Materials for next generation LEDs and lasers:

Limasol, Cyprus, 2022 October 3rd - 5th

Organizers: Maksym Kovalenko, Maryna Bodnarchuk and Grigorios Itskos

Oral, Andriy Stelmakh, presentation 007
DOI: https://doi.org/10.29363/nanoge.emlem.2022.007
Publication date: 15th July 2022

Versatile surface functionalization of highly ionic surfaces, ubiquitous among inorganic nanomaterials, remains a formidable challenge in the view of inherently non-covalent surface bonding.[1] Colloidal lead halide perovskite nanocrystals (NCs), which are of interest for classical and quantum light generation,[2,3] are one of the examples. Despite some recent empirical progress in surface chemistry of lead halide perovskite NCs, the general strategy towards their robust surface functionalization still remains a challenge. In this study we present the first structural investigation of perovskite surfaces capped with zwitterionic phospholipid molecules. In line with molecular dynamics simulations and solid-state NMR, zwitterionic phospholipid ligands bind to the perovskite surfaces with both head-groups, thus hindering their desorption. Furthermore, the ligand head-group affinity to the surface is primarily governed by geometric fitness of its cationic and anionic moieties into the crystal lattice. As a result, stable and colloidally robust nanocrystals of inherently soft and chemically labile lead halide perovskites – FAPbX₃ and MAPbX₃ (X – Br, I) – can be obtained with a lattice-matched phosphoethanolamine head-group. Stable surface passivation is also reflected in excellent optical properties of the NCs. As an example, alkylphospholipid-capped FAPbBr₃ NCs display a stable emission with near unity photoluminescence quantum yield in a broad concentration range, as well as in thick films. Ligand tail engineering, on the other hand, allows diverse surface functionalization of the NCs, broadening the scope of their potential applications.

References:

[1] Akkerman, Q.A.; Rainò, G.; Kovalenko, M.V.; Manna, L. Genesis, Challenges and Opportunities for Colloidal Lead Halide Perovskite Nanocrystals. Nature Mater. 2018, 17, 394-405.

[2] Liu, M. et al. Suppression of Temperature Quenching in Perovskite Nanocrystals for Efficient and Thermally Stable Light-Emitting Diodes. Nat. Photonics 2021, 15, 379-385.

[3] Rainò, G.; Becker, M.A.; Bodnarchuk, M.I.; Mahrt, R.F.; Kovalenko, M.V.; Stöferle, T. Superfluorescence from Lead Halide Perovskite Quantum Dot Superlattices. Nature 2018, 563, 671-675.

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