TY - JOUR
T1 - Resolving the Heat Generated from ZrO2 Atomic Layer Deposition Surface Reactions
AU - Bielinski, Ashley R.
AU - Kamphaus, Ethan P.
AU - Cheng, Lei
AU - Martinson, Alex B.F.
N1 - Publisher Copyright:
© 2023 The Authors. Published by Wiley-VCH GmbH.
PY - 2023/7/24
Y1 - 2023/7/24
N2 - 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.
AB - 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.
KW - Atomic Layer Deposition
KW - Calorimetry
KW - Surface Chemistry
UR - http://www.scopus.com/inward/record.url?scp=85161657529&partnerID=8YFLogxK
U2 - 10.1002/anie.202301843
DO - 10.1002/anie.202301843
M3 - Article
C2 - 37316957
AN - SCOPUS:85161657529
SN - 1433-7851
VL - 62
JO - Angewandte Chemie - International Edition
JF - Angewandte Chemie - International Edition
IS - 30
M1 - e202301843
ER -