Abstract The 2D semiconductor monolayer MoS 2 is expected to be a potential channel material to achieve higher miniaturization and integration in post‐Moore era due to its exceptional electrical and optical properties. However, the weak van der Waals interaction between MoS 2 and the dielectric substrate induces high interfacial thermal resistance and impedes the heat dissipation, leading to significant temperature rise and consequential device performance degradation. Here, self‐assembled monolayers (SAM) are employed to modify the surface of dielectric SiO 2 and enhance thermal boundary conductance (TBC) between MoS 2 and dielectric layer. The surface roughness of dielectric SiO 2 is improved by the SAM, depressing the photon scattering. More importantly, the interfacial bonding force is strengthened by the formation of chemical covalent N‐Mo bonds between NH 2 ‐terminated SAM and MoS 2, thus leading to a 118% TBC improvement between MoS 2 and NH 2 ‐terminated SiO 2 compared to pristine SiO 2 substrate. Simultaneously, the current reduction caused by self‐heating effect in the monolayer MoS 2 field‐effect transistor is eliminated and the maximum power density of the device is largely improved. The incorporation of SAM in 2D semiconductor nanoelectronics presents great potential for device thermal management and reliability improvement.
