Atomically thin transition metal dichalcogenides (TMDCs) have attracted great interest as a new class of two-dimensional (2D) direct band gap semiconducting materials. The controllable modulation of optical and electrical properties of TMDCs is of fundamental importance to enable a wide range of future optoelectronic devices. Here we demonstrate a modulation of the optoelectronic properties of 2D TMDCs, including MoS2, MoSe2, and WSe2, by interfacing them with two metal-centered phthalocyanine (MPc) molecules: nickel Pc (NiPc) and magnesium Pc (MgPc). We show that the photoluminescence (PL) emission can be selectively and reversibly engineered through energetically favorable electron transfer from photoexcited TMDCs to MPcs. NiPc molecules, whose reduction potential is positioned below the conduction band minima (CBM) of monolayer MoSe2 and WSe2, but is higher than that of MoS2, quench the PL signatures of MoSe2 and WSe2, but not MoS2. Similarly, MgPc quenches only WSe2, as its reduction potential is situated below the CBM of WSe2, but above those of MoS2 and MoSe2. The quenched PL emission can be fully recovered when MPc molecules are removed from the TMDC surfaces, which may be refunctionalized and recycled multiple times. We also find that photocurrents from TMDCs, probed by photoconductive atomic force microscopy, increase over 2-fold only when the PL is quenched by MPcs, further supporting the photoinduced charge transfer mechanism. Our results should benefit design strategies for 2D inorganic-organic optoelectronic devices and systems with tunable properties and improved performances.
Keywords: optoelectronics; photoconductive AFM; photoinduced charge transfer; photoluminescence; transition metal dichalcogenide; two-dimensional semiconductor.