Surface‐Grown Organic Architectures for Nanoelectronics: From Molecular Design to Device Function

ABSTRACT Surface‐grown organic structures—organic molecules or polymers chemically tethered to substrates—have emerged as versatile platforms for tailoring surface properties and enabling advanced functionalities in nanoscale electronic devices. These structures, formed via surface‐initiated oligomerization or polymerization, offer precise control over parameters such as surface energy, wettability, and biocompatibility, making them indispensable in applications ranging from sensors and microfluidics to organic semiconductors and antifouling coatings. In the realm of organic and flexible electronics, polymer brushes derived from surface‐grown architectures exhibit enhanced stability and tunable electronic properties, distinguishing them from their free polymer counterparts. This review provides a comprehensive overview of surface‐grown organic structures for applications in nanoscale electronic devices. We first explore the charge transport mechanisms in surface‐initiated oligomers and polymers, highlighting the transition from tunneling to hopping in oligomers and the influence of molecular alignment and morphology on charge mobility in conjugated polymers. Next, we examine the synthetic strategies and chemical methodologies employed in constructing these structures, including dipping, electrografting, click reactions, and advanced polymerization techniques such as SI‐ATRP, SI‐RAFT, and hybrid grafting approaches. Finally, we delve into their integration into nanoelectronic devices, encompassing sensors, field‐effect transistors, light‐emitting diodes, photovoltaic cells, memory resistors, rectifiers, triboelectric and thermoelectric materials, and spin valves.