Lead halide perovskites nanocrystals have emerged as a leading candidate in perovskite solar cells and light-emitting diodes. Given their favorable, tunable optoelectronic properties through modifying the size of nanocrystals, it is imperative to understand and control the growth of lead halide perovskite nanocrystals. However, during the nanocrystal growth into bulk films, the effect of halide bonding on growth kinetics remains elusive. To understand how a chemical bonding of Pb-X (covalency and ionicity) impact on growth of nanocrystals, we have examined two different halide perovskite nanocrystals of CsPbCl3 (more ionic) and CsPbI3 (more covalent) derived from the same parent CsPbBr3 nanocrystals. Tracking the growth of nanocrystals by monitoring the spectral features of bulk peaks (at 445 nm for Cl and at 650 nm for I) enables us to determine the growth activation energy to be 92 kJ/mol (for CsPbCl3 ) versus 71 kJ/mol (for CsPbI3 ). The electronegativity of halides in Pb-X bonds governs the bond strength (150-240 kJ/mol), characteristics of bonding (ionic versus covalent), and growth kinetics and resulting activation energies. A fundamental understanding of Pb-X bonding provides a significant insight into controlling the size of the perovskite nanocrystals with more desired optoelectronic properties.
Keywords: bonding characteristic; carrier dynamics; growth kinetics; nanocrystal growth; perovskite nanocrystals.
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