Energetic hot electrons from exciton-to-hot electron upconversion in Mn-doped semiconductor nanocrystals

Generation of hot electrons and their utilization in photoinduced chemical processes have been the subjects of intense research in recent years mostly exploring hot electrons in plasmonic metal nanostructures created via decay of optically excited plasmon. Here, we present recent progress made in generation and utilization of a different type of hot electrons produced via biphotonic exciton-to-hot electron "upconversion" in Mn-doped semiconductor nanocrystals. Compared to the plasmonic hot electrons, those produced via biphotonic upconversion in Mn-doped semiconductor nanocrystals possess much higher energy, enabling more efficient long-range electron transfer across the high energy barrier. They can even be ejected above the vacuum level creating photoelectrons, which can possibly produce solvated electrons. Despite the biphotonic nature of the upconversion process, hot electrons can be generated with weak cw excitation equivalent to the concentrated solar radiation without requiring intense or high-energy photons. This perspective reviews recent work elucidating the mechanism of generating energetic hot electrons in Mn-doped semiconductor nanocrystals, detection of these hot electrons as photocurrent or photoelectron emission, and their utilization in chemical processes such as photocatalysis. New opportunities that the energetic hot electrons can open by creating solvated electrons, which can be viewed as the longer-lived and mobile version of hot electrons more useful for chemical processes, and the challenges in practical utilization of energetic hot electrons are also discussed.