Water Dose influence to the ALD hafnium oxide process: Simulation and experiment

Abstract

In this work, we report a two-dimensional gas-dynamic model for the formation of hafnium oxide from TDMAH and water during the atomic layer deposition (ALD) process. Application of the model is demonstrated by the example of water cycle, in which the monolayer of functional groups –OH is formed. The simulation results show that the duration of the water pulse affects the dynamics of surface coverage with the -OH groups. At short pulse durations, the resulting coverage of the film surface with -OH groups becomes incomplete and has heterogeneous distribution over the film surface, which is due to the design of the reaction chamber and regimes of gas supply. The amount of residual water vapor depends on the duration of the water pulse and pumping regimes. Experimental data show the influence of water pulse duration on the refractive index, which is related to the structure of the deposited layer (composition, morphology, etc.). Based on experimental data and modeling results, we explain the effect of water pulse duration on the refractive index by the change in reaction mechanisms depending on water amount in the chamber. With a lack of water, the incomplete monolayer of –OH groups is formed and a {HfO2-y} layer grows as a result of the monomolecular decomposition of the precursor. With an excess of water, we expect the implementation of multilayer adsorption of water, provoking the reaction of the precursor in the volume of the water film, leading to the formation of the product {HfO2+y}.