Singha Prajit Kumar, Mukhopadhyay Tamoghna, Tarif Ejaj, Ali Fariyad, Datta Anindya
Department of Chemistry, Indian Institute of Technology Bombay, Powai, Mumbai 400076, India.
J Chem Phys. 2024 Aug 7;161(5). doi: 10.1063/5.0205940.
Single particle level microscopy of immobilized FAPbBr3 nanocrystals (NCs) has elucidated the involvement of different processes in their photoluminescence (PL) intermittency. Four different blinking patterns are observed in the data from more than 100 NCs. The dependence of PL decays on PL intensities brought out in fluorescence lifetime intensity distribution (FLID) plots is rationalized by the interplay of exciton- and trion-mediated recombinations along with hot carrier (HC) trapping. The high intensity-long lifetime component is attributed to neutral exciton recombination, the low intensity-short lifetime component is attributed to trion assisted recombination, and the low intensity-long lifetime component is attributed to hot carrier recombination. Change-point analysis (CPA) of the PL blinking data reveals the involvement of multiple intermediate states. Truncated power law distribution is found to be more appropriate than power law and lognormal distribution for on and off events. Probability distributions of PL trajectories of single NCs are obtained for two different excitation fluences and wavelengths (λex = 400, 440 nm). Trapping rate (kT) prevails at higher power densities for both excitation wavelengths. From a careful analysis of the FLID and probability distributions, it is concluded that there is competition between the HC and trion assisted blinking pathways and that the contribution of these mechanisms varies with excitation wavelength as well as fluence.
固定化FAPbBr₃纳米晶体(NCs)的单粒子水平显微镜研究阐明了不同过程在其光致发光(PL)间歇性中的作用。在来自100多个NCs的数据中观察到四种不同的闪烁模式。荧光寿命强度分布(FLID)图中显示的PL衰减对PL强度的依赖性,通过激子和三重子介导的复合以及热载流子(HC)俘获的相互作用得到合理解释。高强度 - 长寿命成分归因于中性激子复合,低强度 - 短寿命成分归因于三重子辅助复合,而低强度 - 长寿命成分归因于热载流子复合。PL闪烁数据的变点分析(CPA)揭示了多个中间态的参与。对于开和关事件,发现截断幂律分布比幂律和对数正态分布更合适。获得了两种不同激发通量和波长(λex = 400、440 nm)下单NCs的PL轨迹的概率分布。对于两种激发波长,在较高功率密度下俘获率(kT)占主导。通过对FLID和概率分布的仔细分析,得出结论:HC和三重子辅助闪烁途径之间存在竞争,并且这些机制的贡献随激发波长和通量而变化。