Abstract
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.
| Original language | English |
|---|---|
| Article number | e202301843 |
| Journal | Angewandte Chemie - International Edition |
| Volume | 62 |
| Issue number | 30 |
| DOIs | |
| State | Published - Jul 24 2023 |
| Externally published | Yes |
Funding
This work was supported by the U.S. Department of Energy, Office of Science, Basic Energy Sciences, Materials Science and Engineering Division. A.R.B. acknowledges support through the Maria Goeppert Mayer Fellowship, which is supported by the Laboratory Directed Research and Development (LDRD) funding from Argonne National Laboratory, provided by the Director, Office of Science, U.S. Department of Energy under contract No. DE‐AC02‐06CH11357.
Keywords
- Atomic Layer Deposition
- Calorimetry
- Surface Chemistry