Molecular Fin Effect from Heterogeneous Self-Assembled Monolayer Enhances Thermal Conductance across Hard–Soft Interfaces

Thermal transport across hard-soft interfaces is critical to many modern applications, such as composite materials, thermal management in microelectronics, solar-thermal phase transition, and nanoparticle-assisted hyperthermia therapeutics. In this study, we use equilibrium molecular dynamics (EMD) simulations combined with the Green-Kubo method to study how molecularly heterogeneous structures of the self-assembled monolayer (SAM) affect the thermal transport across the interfaces between the SAM-functionalized gold and organic liquids (hexylamine, propylamine and hexane). We focus on a practically synthesizable heterogeneous SAM featuring alternating short and long molecular chains. Such a structure is found to improve the thermal conductance across the hard-soft interface by 46-68% compared to a homogeneous nonpolar SAM. Through a series of further simulations and analyses, it is found that the root reason for this enhancement is the penetration of the liquid molecules into the spaces between the long SAM molecule chains, which increase the effective contact area. Such an effect is similar to the fins used in macroscopic heat exchanger. This "molecular fin" structure from the heterogeneous SAM studied in this work provides a new general route for enhancing thermal transport across hard-soft material interfaces.