A model-based methodology for the analysis and design of atomic layer deposition processes—Part I: Mechanistic modelling of continuous flow reactors

This paper presents the development of an experimentally validated model that mechanistically comprehends the complex interaction between the gas-phase fluid dynamics, the mass transport of individual species, and the heterogeneous gas–surface reaction mechanism in a continuous cross-flow atomic layer deposition (ALD) reactor. The developed ALD gas–surface reaction mechanism, purely based on consecutive and parallel elementary Eley–Rideal reaction steps, was incorporated into the computational fluid dynamic representation of the equipment-scale. Thereby, the model mechanistically relates local gas-phase conditions in the vicinity of the substrate surface to the transient production and consumption of the fractional surface coverage of chemisorbed species, ultimately underlying epitaxial film growth. The model is oriented towards optimization and control and enables identification of substrate film thickness uniformity sensitivities to process operating parameters, reactor system design and gas flow distribution. For the experimental validation of the derived mathematical model, a detailed experimental investigation with the focus on the impact of process operating parameters on the spatial evolution of ZnO film thickness profile was performed. The controlled deposition of ZnO from Zn(C2H5)2 and H2O was carried out in the continuous cross-flow ALD reactor system F-120 by ASM Microchemistry Ltd. and ex situ film thickness measurements at a discrete set of sampling positions on the substrate were performed using X-ray reflectivity and X-ray fluorescence analysis. The experimental results reported here, underscore the importance of substrate-scale uniformity measurements in developing mechanistic ALD process models with high predictability of the dynamic evolution of the spatially dependent film thickness profile. The experimental validation and extensive mechanistic analysis of the ALD reactor model are presented in the second article of this series ( Holmqvist et al., in press).

► Development of an experimentally validated continuous flow ALD reactor model. ► ALD reaction mechanism is based on consecutive and parallel elementary Eley–Rideal reaction steps. ► The model provides extensive real-time quantitative information regarding reactor conditions. ► Experimental investigation with focus of the impact of process operating parameters. ► Case study on deposition of ZnO films from Zn(C2H5)2 and H2O in a continuous flow reactor.