Conditions for electronic hybridization between transition-metal dichalcogenide monolayers and physisorbed carbon-conjugated molecules

Abstract

Abstract Hybridization effects play a crucial role in determining the electronic properties of hybrid inorganic/organic interfaces. To gain insight into these important interactions, we perform a first-principles study based on hybrid density-functional theory including spin–orbit coupling, focusing on eight representative systems formed by two carbon-conjugated molecules—pyrene and perylene—physisorbed on the transition-metal dichalcogenide monolayers (TMDCs) MoS2, MoSe2, WS2, and WSe2. By means of band unfolding techniques, we analyze the band structures of the considered materials, identifying the contributions of the individual constituents as well as the signatures of their hybridization. Based on symmetry and energetic arguments, we derive general conditions for electronic hybridization between conjugated molecules and underlying TMDCs even when the former do not lie planar on the latter, thus providing the key to predict how their mutual arrangement affect their electronic interactions.