Three-Dimensional Spirothienoquinoline-Based Small Molecules for Organic Photovoltaic and Organic Resistive Memory Applications

A new electron-rich spirothienoquinoline unit, ^tBuSAF-Th, has been developed via incorporation of a thienyl unit instead of a phenyl unit into the six-membered ring of the spiroacridine (SAF) and utilized for the first time as a building block for constructing small-molecule electron donors in organic solar cells (OSCs) and as active layers in organic resistive memory devices. The resulting three-dimensional spirothienoquinoline-containing 1-4 exhibit high-lying highest occupied molecular orbital (HOMO) energy levels. By the introduction of electron-deficient benzochalcogenodiazole linkers, with the chalcogen atoms being varied from O to S and Se, a progressively lower lowest unoccupied molecular orbital (LUMO) energy level has been achieved while keeping the HOMO energy levels similar. This strategy has allowed an enhanced light-harvesting ability without compromising open-circuit voltage (V_oc) in vacuum-deposited bulk heterojunction OSCs using 1-4 as donors and C₇₀ as the acceptor. Good photovoltaic performances with power conversion efficiencies (PCEs) of up to 3.86% and high short-circuit current densities (J_sc) of up to 10.84 mA cm^-2 have been achieved. In addition, organic resistive memory devices fabricated with these donor-acceptor small molecules exhibit binary logic memory behaviors with long retention times and high on/off current ratios. This work indicates that the spirothienoquinoline moiety is a potential building block for constructing multifunctional organic electronic materials.