Thermal transport of amorphous hafnia across the glass transition

Abstract

Heat transport in glasses across a wide range of temperature is vital for applications in gate dielectrics and heat insulator. However, it remains poorly understood due to the challenges of modeling vibrational anharmonicity below glass transition temperature and capturing configurational dynamics across the transition. Interestingly, recent calculations predicted that amorphous hafnia (a-HfO$_2$) exhibits an unusual drop in thermal conductivity ($\kappa$) with temperature, contrasting with the typical rise or saturation observed in glasses upon heating. Using molecular dynamics simulations with a machine-learning-based neuroevolution potential, we compute the vibrational properties and $\kappa$ of a-HfO$_2$ from 50~K to 2000~K. At low temperatures, we employ the Wigner transport equation to incorporate both anharmonicity and Bose-Einstein statistics of atomic vibration in the calculation of $\kappa$. At above 1200~K, atomic diffusion breaks down the Lorentzian-shaped quasiparticle picture and makes the lattice-dynamics treatment invalid. We thus use molecular dynamics with the Green-Kubo method to capture convective heat transport in a-HfO$_2$ near the glass transition at around 1500~K. Additionally, by extending the Wigner transport equation to supercooled liquid states, we find the crucial role of low-frequency modes in facilitating heat convection. The computed $\kappa$ of a-HfO$_2$, based on both Green-Kubo and Wigner transport theories, reveals a continuous increase with temperature up to 2000~K.