Thermal and Thermoelectric Properties of SAM-Based Molecular Junctions

In molecular thermoelectrics, the thermopower of molecular junctions is closely interlinked with their thermal properties; however, the detailed relationship between them remains uncertain. This study systematically investigates the thermal properties of self-assembled monolayer (SAM)-based molecular junctions and relates them to the thermoelectric performance of the junctions. The electrode temperatures for the bare Au^TS, Au^TS/EGaIn, and Au^TS/TPT SAM//Ga₂O₃/EGaIn samples placed on a hot chuck were measured under different conditions, such as air vs vacuum and the presence and absence of thermal grease, which generates a heat conduction channel from a hot chuck to gold. It was revealed that the SAM was the most efficient thermal resistor, which was responsible for the creation of a temperature differential (ΔT) across the junction; ΔT in an air atmosphere is overestimated to some extent, and air mainly contributes to large dispersions of thermovoltage (ΔV) data. While junction measurements in air were possible at low ΔT (up to 13 K), the new optimal condition, under a vacuum and with thermal grease, allowed us to examine a wide temperature range up to ΔT = 40 K and obtain a more reliable Seebeck coefficient (S, μV/K). The value of S under the new condition was ∼1.4 times higher than that measured in air without thermal grease. Our study shows the potential of liquid-metal-based junctions to reliably investigate heat conduction across nanometer-thick organic films and elaborates on how the thermal properties of molecular junctions affect their thermoelectric performance.