Resolving the Heat Generated from ZrO2 Atomic Layer Deposition Surface Reactions.
Ashley R Bielinski1, Ethan P Kamphaus1, Lei Cheng1
1Materials Science Division, Argonne National Laboratory, Lemont, IL-60439, USA.
Angewandte Chemie (International Ed. in English)
|June 14, 2023
Summary
This study used in situ pyroelectric calorimetry to analyze atomic layer deposition (ALD) of zirconium oxide. Calorimetry revealed insights into the thermodynamics and kinetics of surface reactions for TDMAZr and water precursors.
Area of Science:
- Materials Science
- Surface Chemistry
- Chemical Engineering
Background:
- Atomic Layer Deposition (ALD) is a crucial technique for thin film fabrication.
- Understanding the surface reactions in ALD is key to controlling film properties.
- Zirconium oxide (ZrO2) is a widely used material in microelectronics and optics.
Purpose of the Study:
- To investigate the thermodynamics and kinetics of surface reactions during ZrO2 ALD.
- To gain insights into the reaction mechanisms using in situ calorimetry and ellipsometry.
- To explore the influence of surface hydration on reaction thermodynamics.
Main Methods:
- In situ pyroelectric calorimetry for time-resolved heat measurements.
- Spectroscopic ellipsometry for surface characterization.
- Density Functional Theory (DFT) methods for computational investigation.
Main Results:
- Calibrated in situ ALD calorimetry provided detailed thermodynamic and kinetic data.
- Net ALD reaction heat was measured between 0.155 and 0.197 mJ/cm², averaging 4.0 eV/Zr.
- No significant temperature dependence for reaction kinetics was observed within the studied range.
Conclusions:
- The study elucidates the thermodynamics of saturating surface reactions in ZrO2 ALD.
- Temperature dependence of reaction heat is linked to growth rate and surface hydroxylation.
- Computational DFT studies enhance understanding of surface hydration effects on reaction thermodynamics.
