Validation of the Wiedemann-Franz Law in Solid and Molten Tungsten above 2000 K through Thermal Conductivity Measurements via Steady-State Temperature Differential Radiometry.

We measure the thermal conductivity of solid and molten tungsten using steady state temperature differential radiometry. We demonstrate that the thermal conductivity can be well described by application of Wiedemann-Franz law to electrical resistivity data, thus suggesting the validity of Wiedemann-Franz law to capture the electronic thermal conductivity of metals in their molten phase. We further support this conclusion using ab initio molecular dynamics simulations with a machine-learned potential. Our results show that at these high temperatures, the vibrational contribution to thermal conductivity is negligible compared to the electronic component.

Chemical, Structural, and Electrical Changes in Molecular Layer-Deposited Hafnicone Thin Films after Thermal Processing.

Post deposition annealing of molecular layer-deposited (MLD) hafnicone films was examined and compared to that of hafnium oxide atomic layer-deposited (ALD) films. Hafnicone films were deposited using tetrakis(dimethylamido)hafnium (TDMAH), and ethylene glycol and hafnia films were deposited using TDMAH and water at 120 °C. The changes in the properties of the as-deposited hafnicone films with annealing were probed by various techniques and then compared to the as-deposited and annealed ALD hafnia films. In situ X-ray reflectivity indicated a 70% decrease in thickness and ∼100% increase in density upon heating to 400 °C yet the density remained lower than that of hafnia control samples. The largest decreases in thickness of the hafnicone films were observed from 150 to 350 °C. In situ X-ray diffraction indicated an increase in the temperature required for crystallization in the hafnicone films (600 °C) relative to the hafnia films (350 °C). The changes in chemistry of the hafnicone films annealed with and without UV exposure were probed using Fourier transformed infrared spectroscopy and X-ray photoelectron spectroscopy with no significant differences attributed to the UV exposure. The hafnicone films exhibited lower dielectric constants than hafnia control samples over the entire temperature range examined. The CF4/O2 etch rate of the hafnicone films was comparable to the etch rate of hafnia films after annealing at 350 °C. The thermal conductivity of the hafnicone films initially decreased with thermal processing (up to 250 °C) and then increased (350 °C), likely due to porosity generation and subsequent densification, respectively. This work demonstrates that annealing MLD films is a promising strategy for generating thin films with a low density and relative permittivity.