Resolving the Heat Generated from ZrO2 Atomic Layer Deposition Surface Reactions

In situ pyroelectric calorimetry and spectroscopic ellipsometry were used to investigate surface reactions in atomic layer deposition (ALD) of zirconium oxide (ZrO2). Calibrated and time‐resolved in situ ALD calorimetry provides new insights into the thermodynamics and kinetics of saturating surface reactions for tetrakis(dimethylamino)zirconium(IV) (TDMAZr) and water. The net ALD reaction heat ranged from 0.197 mJ cm−2 at 76 °C to 0.155 mJ cm−2 at 158 °C, corresponding to an average of 4.0 eV/Zr at all temperatures. A temperature dependence for reaction kinetics was not resolved over the range investigated. The temperature dependence of net reaction heat and distribution among metalorganic and oxygen source exposure is attributed to factors including growth rate, equilibrium surface hydroxylation, and the extent of the reaction. ZrO2‐forming surface reactions were investigated computationally using DFT methods to better understand the influence of surface hydration on reaction thermodynamics. In situ pyroelectric calorimetry was used to investigate the saturating surface reactions for tetrakis(dimethylamino)zirconium(IV) (TDMAZr) and water. Time‐resolved measurements of heat generation provide both kinetic and thermodynamic information. These results were compared to calculated enthalpies from DFT models to better understand proposed mechanisms for these atomic layer deposition (ALD) reactions.