Modulating the Conduction Band Energies of Si Electrode Interfaces Functionalized with Monolayers of a Bay-Substituted Perylene Bisimide

The confinement of π-conjugated chromophores on silicon (Si) electrode surfaces is a powerful approach to engineer electroresponsive monolayers relevant to microelectronics, electrocatalysis, and information storage and processing. While common strategies to functionalize Si interfaces exploit molecularly dissolved building blocks, only a handful number of studies have leveraged the structure-function relationships of π-aggregates to tune the electronic structures of hybrid monolayers at Si interfaces. Herein, we show that the semiconducting properties of n-type monolayers constructed on Si electrodes are intimately correlated to the initial aggregation state of π-conjugated chromophore precursors derived from bay-substituted perylene bisimide (PBI) units. Specifically, our study unravels that for n-type monolayers engineered using PBI π-aggregates, the cathodic reduction potentials required to inject negative charge carriers into the conduction bands can be stabilized by 295 mV through reversible switching of the maximum anodic potential (MAP) that is applied during the oxidative cycles (+0.5 or +1.5 V vs Ag/AgCl). This redox-assisted stabilization effect is not observed with n-type monolayers derived from molecularly dissolved PBI cores and monolayers featuring a low surface density of the redox-active probes. These findings unequivocally point to the crucial role played by PBI π-aggregates in modulating the conduction band energies of n-type monolayers where a high MAP of +1.5 V enables the formation of electronic trap states that facilitate electron injection when sweeping back to cathodic potentials. Because the structure-function relationships of PBI π-aggregates are shown to modulate the semiconducting properties of hybrid n-type monolayers constructed at Si interfaces, our results hold promising opportunities to develop redox-switchable monolayers for engineering nonvolatile electronic memory devices.