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Area selective deposition (ASD) strategies are broadly enabling, where their application is anticipated to impact semiconductor scaling, in the short term, and broadly impact the design of non-traditional hardware such as phase change memory for specialized artificial intelligence (AI) hardware. In order to extend scaling, ASD may be required for the formation of self-aligned structures on patterned substrates that enable schemes, such as fully aligned via. The design of inhibiting materials including small molecule, polymer brushes and area selective surface polymerizations can be tailored to enable the selective deposition of a variety of metal oxide films (e.g., Al2O3, TiO2 or ZnO). The inhibiting materials examined systematically varied inhibitor spacing, composition and surface cleans prior to inhibitor deposition. The examination of a range of materials provides insight into the fundamental mechanisms of inhibition between precursor chemistries and their interaction with surfaces. Furthermore, while the materials generally exploited for inhibition are relegated to small molecules and may require multiple cycles of etch-back processes followed by renewal of the surface inhibitor polymeric materials may offer the potential to access ASD of films with devices that have significant surface topography where they act as effective inhibitors over small molecules. This was achieved with the area selective growth of polymers where the area selective control of a polymerization on a 100nm tall copper line space feature enabled the selective deposition on a silicon dielectric. In addition, while the ASD of some film compositions could not be achieved with polymer inhibitors the ALD on polymer regions of a patterned film increased the porosity of the metal oxide changing the film’s etch resistance, this could be exploited to achieve the area selective etch of metal features.
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