The design of optimal sequences for multicomponent ALD processes can be a time-consuming procedure: transient effects can appear each time that one switches to a different precursor, making it hard to predict beforehand the desired composition. Consequently, researchers usually resort to trial runs to calibrate the film composition, and combination of precursors with well-behaved nucleation behaviors and fast transients are highly prized. While effective for processes involving two different precursors, this empirical approach makes it hard to extend ALD to explore more complex materials involving ternary or quaternary compounds.In this work we explore an alternative approach that uses machine learning integrated with in-situ techniques to optimize the composition of multicomponent films. Our approach relies on digital twins to train, optimize, and benchmark algorithms that build the sequence of ALD cycles in real time from the feedback of in-situ data. These models allow us to generate a wide range of processes with different types of nucleation behaviors, providing the ideal testbed for the development of robust algorithms. We then transfer these algorithms into our experimental reactors for the exploration and optimization of processes involving two and three different types of oxide materials. Our results show that it is possible to drive the optimization of binary and ternary ALD processes using solely the growth per cycle of the individual processes as input, with the algorithm being robust across different nucleation behaviors. The main limitation of the proposed approach is that, for techniques showing a net change in the material, such as quartz crystal microbalance, it is not possible to consider systems that exhibit a substantial amount of etching, such the ZnO/Al2O3 process involving diethyl zinc and trimethyaluminum precursors. This would not be a limitation for techniques providing direct compositional information, such as X-ray fluorescence, or those focusing on materials properties, such as in-situ spectroscopic ellipsometry.This research is based on the work supported by the Laboratory Directed Research and Development (LDRD) funding from the Argonne National Laboratory, provided by the Director, Office of Science, of the U.S. DOE under Contract No. DE-AC02-06CH11357.
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