Ultrafast electronic relaxation processes in semiconductor nanoparticles (silver iodide, silver iodide/silver sulfide, silver bromide/silver sulfide, silver sulfide, cupric sulfide, and copper sulfide) and carotenoids

This dissertation examines primarily the ultrafast dynamics of excited state charge carriers in semiconductor nanoparticles. The dissertation also briefly examines the excited state lifetimes of a few carotenoids. Understanding the dynamic properties of charge carriers in semiconductor nanoparticles is crucial for the further development of applications utilizing these systems. The dynamic properties including shallow and deep trapping as well as recombination have been studied in a variety of semiconductor nanoparticle systems. Kinetic modeling was utilized to assist in the assignment of all observed signals and the nature of the decays. The first observation of ultrafast trapping in silver halides was observed in AgI nanoparticles including the identification that interstitial silver ions may act as deep traps. Several interesting phenomena were observed in Ag2S and CuxS nanoparticles including dark shallow trap states and shallow trap state saturation leading to increased transient absorption over transient bleach with increasing excitation intensity. These observations have provided further insight into the relaxation pathways for charge carriers in semiconductor nanoparticle systems. Lifetimes of the S2 excited states of four carotenoids have also been determined. The S2 lifetime for beta-carotene was confirmed from previous fluorescence up-conversion experiments whereas the S2 lifetimes that were previously unknown for three carotenoids, violaxanthin, neaxanthin, and lutein were discovered. These experiments together demonstrate the capabilities of femtosecond pump-probe spectroscopy to characterize and better understand the processes involved in the ultrafast relaxation events in both molecular and nanoparticle systems.