Engineering Molecular Rectification: Mechanisms, Modulation Strategies, and Device Integration

Molecular rectifiers, as prototypical components of molecular electronics, present unique opportunities for pushing device miniaturization to its ultimate limits. Nevertheless, challenges including limited rectification ratios (RR), insufficient robustness, and poor reproducibility impede their practical deployment. To make molecular rectifiers competitive with silicon-based devices, it is important to fully understand the design principles and fabrication methods from both mechanistic and experimental perspectives. By holistically considering the transport mechanisms, modulation strategies, fabrication, characterization techniques, and theoretical simulations, this review provides a comprehensive overview of molecular rectifiers. Representative examples of conceptually significant and high-performance molecular rectifier systems are highlighted to illustrate the relationships between rectification mechanisms, molecular design strategies, and device realization. Building on these discussions, we present an outlook for current bottlenecks and future directions to guide the development of molecular rectifiers. This review aims to serve as both a conceptual framework and a technical reference for researchers working at the intersection of molecular electronics and nanoscale device engineering in the post-CMOS era.