Transforming exciton dynamics in perovskite nanocrystal through Mn doping

Zn-alloyed CsPb(Cl/Br)₃ perovskite nanocrystals (PNCs) have been synthesized and used as a model system for Mn doping in order to understand the effect of Mn doping on exciton dynamics. While keeping the PL emission maximum and PLQY of both PNC samples nearly the same, the radiative decay rate of the host band decreases ∼6.5 times and the non-radiative decay rate increases ∼2.5 times upon Mn doping. Unlike reports in the literature in which the dopant emission decreases to near-zero, in the present case we observe ∼5.5-fold enhancement of the integrated PL intensity of the dopant emission when the temperature decreases from 290 K to 190 K. Interestingly, the FWHM of the host PL emission band increases with a decrease in temperature from 290 K to 190 K. A higher value of phonon energy in PNC2 (58 ± 2 meV) in comparison to CsPbBr₃ has been noted. The low magnitude of the Huang-Rhys factor indicates less electron phonon coupling for the Mn-doped PNC system. Temperature-dependent dopant PL decay exhibits biexponential decay behaviour with time constants τ₁ = 450-540 μs and τ₂ = 1.1-1.2 ms. With a decrease in temperature from 290 K to 190 K, the amplitude of the faster component decreases from 80% to 60%; concomitantly, the amplitude of the slower component increases from 20% to 40%. Ultrasensitive single-particle spectroscopic analyses reveal that, although the probability density distributions (PDDs) of the durations of both ON and OFF events of PNC1 could be fitted with a truncated inverse power law (TIPL), however, for PNC2, both PDDs could be fitted with an inverse power law (IPL). A comparatively lower value of the power law exponent m_ON indicates a higher probability of longer ON events for PNC1 than for PNC2. Truncation in the PDDs of both ON and OFF events has been observed for PNC1, but not in the PDDs of either ON or OFF events for PNC2. The presence of shallow trap states is responsible for the truncation for PNC1, whereas the presence of deep dopant states does not allow truncation in the host PL emission of PNC2. All these observations clearly demonstrate that Mn doping transforms the host PL exciton dynamics for Zn-alloyed Mn-doped CsPb(Cl/Br)₃ PNCs very significantly.