Optical and Magneto-Optical Properties of Donor-Bound Excitons in Vacancy-Engineered Colloidal Nanocrystals.

Carulli, Francesco; Pinchetti, Valerio; Zaffalon, Matteo L; Camellini, Andrea; Rotta Loria, Silvia; Moro, Fabrizio; Fanciulli, Marco; Zavelani-Rossi, Margherita et al. · Nano Lett · 2021

basic_science · Level V

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Abstract

Controlled insertion of electronic states within the band gap of semiconductor nanocrystals (NCs) is a powerful tool for tuning their physical properties. One compelling example is II-VI NCs incorporating heterovalent coinage metals in which hole capture produces acceptor-bound excitons. To date, the opposite donor-bound exciton scheme has not been realized because of the unavailability of suitable donor dopants. Here, we produce a model system for donor-bound excitons in CdSeS NCs engineered with sulfur vacancies (<i>V</i><sub>S</sub>) that introduce a donor state below the conduction band (CB), resulting in long-lived intragap luminescence. <i>V</i><sub>S</sub>-localized electrons are almost unaffected by trapping, and suppression of thermal quenching boosts the emission efficiency to 85%. Magneto-optical measurements indicate that the <i>V</i><sub>S</sub> are not magnetically coupled to the NC bands and that the polarization properties are determined by the spin of the valence-band photohole, whose spin flip is massively slowed down due to suppressed exchange interaction with the donor-localized electron.