Understanding the growth mechanisms of ultrasmall silver selenide quantum dots for short-wave infrared detectors

Colloidal quantum dots (CQDs) allow for wavelength-tunable, economic, and elegant access to the infrared (IR) spectrum by utilizing inter- and intraband excitonic transitions in narrow bandgap semiconductors. With the emergence of new applications for IR detection, developing competitive non-toxic and environmentally benign alternatives to heavy metal-containing semiconductors is of increasing importance. Over the last decade, silver selenide (Ag2Se) has emerged as an alternative to lead- and mercury-based QDs, especially with large, intraband Ag2Se CQDs showing promising performance in the mid-wave IR. Herein we explored the critical nucleation and growth mechanisms of ultrasmall (2.5–3.5 nm) interband absorbing Ag2Se CQDs operating in the near to short-wave IR. Classical nucleation and growth was observed at most reaction conditions, with a growth temperature of 140 °C and a Ag:Se precursor molar ratio of 1:2 providing the most robust control over the IR absorption spectrum. We proceeded to perform an in-depth study of the impact of surface ligand chemistry of CQD thin-films on resulting optoelectronic properties. By tuning the functional groups and optimizing ligand exchange parameters, we obtained IR responsivity values of ∼25 mA/W in photoconductor devices and ∼1.8 mA/W in photodiode devices in the range 800 – 1250 nm.