Tunable Conductance of MoS and WS Quantum Dots by Electron Transfer with Redox-Active Quinone.

Due to their uniqueness in tunable photophysics, transition metal dichalcogenide (TMD) based quantum dots (QDs) have emerged as the next-generation quantum materials for technology-based semiconductor applications. This demands frontline research on the rational synthesis of the TMD QDs with controlled shape, size, nature of charge migration at the interface, and their easy integration in optoelectronic devices. In this article, with a controlled solution-processed synthesis of MoS and WS QDs, we demonstrate the disparity in their structural, optical, and electrical characteristics in bulk and confinement. With a series of steady-state and time-resolved spectroscopic measurements in different media, we explore the uncommon photophysics of MoS and WS QDs such as excitation-dependent photoluminescence and assess their excited state charge transfer kinetics with a redox-active biomolecule, menadione (MQ). In comparison to the homogeneous aqueous medium, photoinduced charge transfer between the QDs and MQ becomes more plausible in encapsulated cetyltrimethylammonium bromide (CTAB) micelles. Current sensing atomic force microscopy (CS-AFM) measurements at a single molecular level reveal that the facilitated charge transfer of QDs with MQ strongly correlates with an enhancement in their charge transport behavior. An increase in charge transport further depends on the density of states of the QDs directing a change in Schottky emission to Fowler-Nordheim (FN) type of tunneling across the metal-QD-metal junction. The selective response of the TMD QDs while in proximity to external molecules can be used to design advanced optoelectronic devices and applications involving rectifiers and tunnel diodes for future quantum technology.