Cross-Plane Thermal Conductance of Phosphonate-Based Self-Assembled Monolayers and Self-Assembled Nanodielectrics.

Self-assembled nanodielectrics (SANDs) consist of alternating layers of polarized phosphonate-functionalized azastibazolium π-electron (PAE) and high-k dielectric metal oxide (ZrO2 or HfOx) films. SANDs are desirable gate dielectrics materials for thin-film transistor applications because of their excellent properties such as low-temperature fabrication, large dielectric strength, and large capacitance. In this paper, we investigate the cross-plane thermal boundary conductance of SANDs using the frequency domain thermoreflectance (FDTR) technique. First, we characterize the thermal conductance of PAE self-assembled monolayers (SAMs), inverted-PAE (IPAE) SAMs, and mixed PAE-IPAE SAMs, sandwiched between thin gold and silica (SiO2) films at the top and bottom surfaces. Next, we quantify the thermal conductance of SAND-n with different numbers (n) of PAE-ZrO2 layers and thicknesses ranging between 4.7 and 11.3 nm. From the FDTR measurements, we observe that the thermal boundary conductance of the SAMs can be tuned between 42.1 ± 4.6 MW/(m2 K) and 52.4 ± 2.5 MW/(m2 K), based on the relative density of the PAE and IPAE chromophores. In the SAND-n samples, we observe a monotonic decrease in the thermal conductance with increasing n. We use the measured thermal conductance data in a series resistance model to estimate a thermal interface conductance of 695 MW/(m2 K) for the contact between the PAE chromophore and the zirconium dioxide films, which is an order of magnitude larger than the SAMs. We attribute the improved thermal conductance to stronger adhesion between the PAE chromophore and the zirconium dioxide films, as compared to the weakly bonded SAMs to the gold and silicon dioxide films.