Insights into the Oxidation State of Cu Dopants in II-VI Semiconductor Nanocrystals

Luminescent Cu-doped semiconductor nanocrystals have played a pivotal role in the emergence of lighting and display applications for a long time. However, consensus regarding the Cu oxidation state and hence their emission mechanism has not been attained. Distinction between seemingly simple optically and magnetically active Cu²⁺ and inactive Cu¹⁺ has surprisingly been the subject matter of debate in the literature for more than a decade. In this Perspective, we first discuss the fundamental quantum mechanical phenomenon explaining the optical properties of the monovalent and divalent Cu dopants. We then focus down on various techniques used to differentiate between these two fundamental mechanisms, their benefits, and their pitfalls arising in large part because of the lack of spatial separation. Hence, to obtain a cohesive story consistent with all the observations, we discuss recent results from single-molecule spectroscopy to understand the optical properties and hence the oxidation state of internally doped Cu in doped nanocrystals.