Yarita Naoki, Tahara Hirokazu, Saruyama Masaki, Kawawaki Tokuhisa, Sato Ryota, Teranishi Toshiharu, Kanemitsu Yoshihiko
Institute for Chemical Research, Kyoto University , Uji, Kyoto 611-0011, Japan.
J Phys Chem Lett. 2017 Dec 21;8(24):6041-6047. doi: 10.1021/acs.jpclett.7b02840. Epub 2017 Dec 4.
We study the origin of photoluminescence (PL) intermittency in formamidinium lead bromide (FAPbBr, FA = HC(NH)) nanocrystals and the impact of postsynthetic surface treatments on the PL intermittency. Single-dot spectroscopy revealed the existence of different individual nanocrystals exhibiting either a blinking (binary on-off switching) or flickering (gradual undulation) behavior of the PL intermittency. Although the PL lifetimes of blinking nanocrystals clearly correlate with the individual absorption cross sections, those of flickering nanocrystals show no correlation with the absorption cross sections. This indicates that flickering has an extrinsic origin, which is in contrast to blinking. We demonstrate that the postsynthetic surface treatment with sodium thiocyanate improves the PL quantum yields and completely suppresses the flickering, while it has no significant effect on the blinking behavior. We conclude that the blinking is caused by Auger recombination of charged excitons, and the flickering is due to a temporal drift of the exciton recombination rate induced by surface-trapped electrons.
我们研究了甲脒溴化铅(FAPbBr₃,FA = HC(NH₂)₂)纳米晶体中光致发光(PL)间歇性的起源以及合成后表面处理对PL间歇性的影响。单点光谱揭示了不同的单个纳米晶体的存在,这些纳米晶体表现出PL间歇性的闪烁(二进制开-关切换)或闪烁(逐渐波动)行为。尽管闪烁纳米晶体的PL寿命与单个吸收截面明显相关,但闪烁纳米晶体的PL寿命与吸收截面无关。这表明闪烁具有非本征起源,这与闪烁形成对比。我们证明,用硫氰酸钠进行合成后表面处理可提高PL量子产率并完全抑制闪烁,而对闪烁行为没有显著影响。我们得出结论,闪烁是由带电激子的俄歇复合引起的,而闪烁是由于表面捕获电子引起的激子复合速率的时间漂移。