Expanding the Chemical and Morphological Space of Lead-Halide Perovskites Nanocrys-tals

Maryna Bodnarchuk^a^,^b, Ihor Cherniukh^a^,^b, Kseniia Shcherbak^a^,^b, Andriy Stelmakh^b^,^a, Leon Feld^b^,^a, Chenglian Zhu^b^,^a, Simon Boehme^b^,^a, Gabriele Rainò^b^,^a, Maksym Kovalenko^b^,^a

^aEmpa-Swiss Federal Laboratories for Materials Science and Technology, 8600 Dübendorf, Switzerland

^bLaboratory of Inorganic Chemistry, Department of Chemistry and Applied Biosciences, ETH Zürich, Switzerland

Proceedings of MATSUS Fall 2025 Conference (MATSUSFall25)

B.8 Emergent Properties in Nanomaterials: Synthesis, Phenomena, and Applications - #EmergentNano

València, Spain, 2025 October 20th - 24th

Organizers: Dmitry Baranov and James Utterback

Invited Speaker, Maryna Bodnarchuk, presentation 228
Publication date: 17th July 2025

The A-site cation in lead-halide perovskite nanocrystals (NCs) plays a pivotal role in fine-tuning their structural and electronic properties. The presently available chemical space remains minimal since, thus far, only three A-site cations, cesium, formamidinium, and methylammonium, have been reported to favor the formation of stable lead-halide perovskite NCs. Inspired by recent reports on bulk single crystals with aziridinium (AZ) as the A-site cation, we present a straightforward colloidal synthesis of AZPbBr₃ NCs with a narrow size distribution and size tunability down to 4 nm, producing quantum dots (QDs) in the regime of strong quantum confinement. NMR and Raman spectroscopies confirm the stabilization of the AZ cations in the locally distorted cubic structure. AZPbBr₃ QDs exhibit bright photoluminescence with quantum efficiencies of up to 80%. Stabilized with cationic and zwitterionic capping ligands, single AZPbBr₃ QDs exhibit stable single-photon emission at both room and cryogenic temperatures, reduced blinking, and high single-photon purity, comparable to the best-reported values for MAPbBr₃ and FAPbBr₃ QDs of the same size.

Beyond compositional engineering, QD shape engineering offers an additional and powerful tool for further fine-tuning and improvement of optical properties, allowing the manipulation of features that are inaccessible by keeping the shape isotropic. In the case of perovskite QDs, shape anisotropy can enable, for example, directional emission, spatial confinement of excitons in one or two dimensions, tuning of exciton fine structure, and radiative decay. To systematically explore shape-dependent properties of one-dimensional CsPbBr3 perovskite structures, we developed a synthetic approach toward stable, size- and shape-uniform nanorods with tunable thickness (5-24 nm) and aspect ratio (1-16, larger for thinner nanorods). By exploiting the difference between {110} and {001} facets of the orthorhombic perovskite structure, we achieved precise control over nanorod morphology. With the use of ligands providing sufficient stability, we performed comprehensive optical characterization, paving the way for advanced optical functionalities in perovskite nanostructures.

References:

[1] Bodnarchuk M.I.; Feld L.G; Zhu C.; Boehme S.C.; Bertolotti F.; Avaro J.; Aebli M.; Mir S.H.;, Masciocchi N.; Erni R.; Chakraborty S.; Guagliardi A.; Rainò G.; Kovalenko M.V. Colloidal Aziridinium Lead Bromide Quantum Dots. ACS Nano 2024, 18 (7), 5684-5697.

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