Quartz Crystal Microbalance Studies of Al2O3 Atomic Layer Deposition Using Trimethylaluminum and Water at 125 °C

Abstract

Al(2)O(3) atomic layer deposition (ALD) growth with Al(CH(3))(3) (trimethylaluminum (TMA)) and H(2)O as the reactants was examined at the relatively low temperature of 125 degrees C using quartz crystal microbalance (QCM) measurements. The total Al(2)O(3) ALD mass gain per cycle (MGPC) and MGPCs during the individual TMA and H(2)O reactions were measured versus TMA and H(2)O exposures. The Al(2)O(3) MGPC increased with increasing H(2)O and TMA exposures at fixed TMA and H(2)O exposures, respectively. However, the TMA and H(2)O reactions were not completely self-limiting. The slower surface reaction kinetics at lower temperature may require very long exposures for the reactions to reach completion. The Al(2)O(3) MGPCs increased quickly versus H(2)O exposure and slowly reached limiting values that were only weakly dependent on the TMA doses. Small TMA exposures were also sufficient for the Al(2)O(3) MGPCs to reach different limiting values for different H(2)O doses. The TMA MGPCs increased for higher TMA exposures at all H(2)O exposures. In contrast, the H(2)O MGPCs decreased for higher TMA exposures at all H(2)O exposures. This decrease may occur from more dehydroxylation at larger hydroxyl coverages after the H(2)O exposures. The hydroxyl coverage after the H(2)O exposure was dependent only on the H(2)O exposure. The Al(2)O(3) MGPC was also linearly dependent on the hydroxyl coverage after the H(2)O dose. Both the observed hydroxyl coverage versus H(2)O exposure and the Al(2)O(3) ALD growth versus H(2)O and TMA exposures were fit using modified Langmuir adsorption isotherm expressions where the pressures are replaced with exposures. These results should be useful for understanding low-temperature Al(2)O(3) ALD, which is important for coating organic, polymeric, and biological substrates.