Towards Aqueous-Soluble Core/Shell Perovskite Nanocrystals

Baptiste Roselli^a, Tuan Minh Duong^a, Stephanie Pouget^b, Wai Li Ling^a, Dmitry Aldakov^a, Peter Reiss^a

^aUniv. Grenoble Alpes, CEA, CNRS, IRIG, SyMMES, F-38000 Grenoble

^bUniv. Grenoble Alpes, CEA, INAC, MEM, 38000 Grenoble, Francia, Grenoble, France

Materials for Sustainable Development Conference (MATSUS)
Proceedings of nanoGe Spring Meeting 2022 (NSM22)

#SNI22. Semiconductor Nanocrystals I: Basic Science (synthesis, spectroscopy, electronic structure, device and application)

Online, Spain, 2022 March 7th - 11th

Organizers: Emmanuel Lhuillier, Sandrine Ithurria and Angshuman Nag

Invited Speaker, Peter Reiss, presentation 294
DOI: https://doi.org/10.29363/nanoge.nsm.2022.294
Publication date: 7th February 2022

Lead halide perovskite nanocrystals (NCs) have drawn tremendous research interest in the past five years fueled by their outstanding optical and electronic properties.[1, 2] In particular CsPbBr₃ NCs exhibit excellent photoluminescence with a very narrow peak and high quantum yield. They can be conveniently synthesized in high yield by means of hot-injection methods.[3-5] However, due to their ionic nature, perovskite NCs are unstable in polar solvents, and when dispersed in water they quickly lose their luminescence properties and chemical integrity.

Many efforts have been undertaken to enhance aqueous stability, encompassing changes in stoichiometry (synthesis under Pb-poor conditions)[6] and encapsulation with appropriate organic compounds or oxides (e.g., block copolymers,[7] SiO₂[8]). On the other hand, the growth of an inorganic shell, as generally applied in the case of conventional nanocrystals/quantum dots, has turned out to be challenging: upon prolonged heating of perovskite NCs, uncontrolled ripening leads to a variety of sizes and shapes. Furthermore, classic shell materials crystallize in different structures and exhibit large lattice mismatches.

Here, we present novel approaches for the growth of metal sulfide and metal oxide shells on CsPbBr₃ nanocrystals, keeping a low size distribution and high fluorescence quantum yield. In the case of metal sulfide shells, aqueous phase transfer of the core/shell NCs could be achieved while maintaining the photoluminescence in water for extended periods. The improved stability of the core/shell perovskite NCs paves the way for their use in various applications such as single-photon emitters and photocatalysis.

References:

[1] Aldakov, D.; Reiss, P., Safer-by-Design Fluorescent Nanocrystals: Metal Halide Perovskites vs Semiconductor Quantum Dots. J. Phys. Chem. C 2019, 123 (20), 12527-12541.

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

[3] Protesescu, L.; Yakunin, S.; Bodnarchuk, M. I.; Krieg, F.; Caputo, R.; Hendon, C. H.; Yang, R. X.; Walsh, A.; Kovalenko, M. V., Nanocrystals of Cesium Lead Halide Perovskites (CsPbX3, X = Cl, Br, and I): Novel Optoelectronic Materials Showing Bright Emission with Wide Color Gamut. Nano Lett. 2015, 15 (6), 3692-3696.

[4] Imran, M.; Caligiuri, V.; Wang, M.; Goldoni, L.; Prato, M.; Krahne, R.; De Trizio, L.; Manna, L., Benzoyl Halides as Alternative Precursors for the Colloidal Synthesis of Lead-Based Halide Perovskite Nanocrystals. Journal of the American Chemical Society 2018, 140 (7), 2656-2664.

[5] Thapa, S.; Bhardwaj, K.; Basel, S.; Pradhan, S.; Eling, C. J.; Adawi, A. M.; Bouillard, J.-S. G.; Stasiuk, G. J.; Reiss, P.; Pariyar, A.; Tamang, S., Long-term ambient air-stable cubic CsPbBr3 perovskite quantum dots using molecular bromine. Nanoscale Advances 2019, 1 (9), 3388-3391.

[6] Chen, K.; Qi, K.; Zhou, T.; Yang, T.; Zhang, Y.; Guo, Z.; Lim, C.-K.; Zhang, J.; Žutic, I.; Zhang, H.; Prasad, P. N., Water-Dispersible CsPbBr3 Perovskite Nanocrystals with Ultra-Stability and its Application in Electrochemical CO2 Reduction. Nano-Micro Letters 2021, 13 (1), 172.

[7] Pramanik, A.; Gates, K.; Patibandla, S.; Davis, D.; Begum, S.; Iftekhar, R.; Alamgir, S.; Paige, S.; Porter, M. M.; Ray, P. C., Water-Soluble and Bright Luminescent Cesium–Lead–Bromide Perovskite Quantum Dot–Polymer Composites for Tumor-Derived Exosome Imaging. ACS Applied Bio Materials 2019, 2 (12), 5872-5879.

[8] Talianov, P. M.; Peltek, O. O.; Masharin, M.; Khubezhov, S.; Baranov, M. A.; Drabavičius, A.; Timin, A. S.; Zelenkov, L. E.; Pushkarev, A. P.; Makarov, S. V.; Zyuzin, M. V., Halide Perovskite Nanocrystals with Enhanced Water Stability for Upconversion Imaging in a Living Cell. J. Phys. Chem. Lett. 2021, 12 (37), 8991-8998.

Acknowledgements:

Univ. Grenoble Alpes IDEX (project IRS C-Super)

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