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In area-selective processes, such as area-selective atomic layer deposition (AS-ALD), there is renewed interest in designing surface modification schemes allowing to tune the reactivity of the nongrowth (NG) substrates. Many efforts are directed toward small molecule inhibitors or atomic layers, which would modify selected surfaces to delay nucleation and provide NG properties in the target AS-ALD processes allowing for the manufacturing of smaller sized features than those produced with alternative approaches. Bromine termination of silicon surfaces, specifically Si(100) and Si(111), is evaluated as a potential pathway to design NG substrates for the deposition of metal oxides, and TiO2 (from cycles of sequential exposures of tetrakis-dimethylamido-titanium and water) is tested as a prototypical deposition material. Nucleation delays on the surfaces produced are comparable to those on H-terminated silicon that is commonly used as an NG substrate. However, the silicon surfaces produced by bromination are more stable, and even oxidation does not change their chemical reactivity substantially. Once the NG surface is eventually overgrown after a large number of ALD cycles, bromine remains at the interface between silicon and TiO2. The NG behavior of different crystal faces of silicon appears to be similar, albeit not identical, despite different arrangements and coverage of bromine atoms. 

As the size of the components in electronic devices decreases, new approaches and chemical modification schemes are needed to produce nanometer-size features with bottom-up manufacturing. Organic monolayers can be used as effective resists to block the growth of materials on non-growth substrates in area-selective deposition methods. However, choosing the appropriate surface modification requires knowledge of the corresponding chemistry and also a detailed investigation of the behavior of the functionalized surface in realistic deposition schemes. This study aims to investigate the chemistry of boronic acids that can be used to prepare such non-growth areas on elemental semiconductors. 4-Fluorophenylboronic acid is used as a model to investigate the possibility to utilize the Si(100) surface functionalized with this compound as a non-growth substrate in a titanium dioxide (TiO2) deposition scheme based on sequential doses of tetrakis(dimethylamido)titanium and water. A combination of X-ray photoelectron spectroscopy and time-of-flight secondary ion mass spectrometry allows for a better understanding of the process. The resulting surface is shown to be an effective non-growth area to TiO2 deposition when compared to currently used H-terminated silicon surfaces but to exhibit much higher stability in ambient conditions. 

Atomically precise and highly selective surface reactions are required for advancing microelectronics fabrication. Advanced atomic processing approaches make use of small molecule inhibitors (SMI) to enable selectivity between growth and nongrowth surfaces. The selectivity between growth and nongrowth substrates is eventually lost for any known combinations, because of defects, new defect formation, and simply because of a Boltzmann distribution of molecular reactivities on surfaces. The selectivity can then be restored by introducing etch-back correction steps. Most recent developments combine the design of highly selective combinations of growth and nongrowth substrates with atomically precise cycles of deposition and etching methods. At that point, a single additional step is often used to passivate the unwanted defects or selected surface chemical sites with SMI. This step is designed to chemically passivate the reactive groups and defects of the nongrowth substrates both before and/or during the deposition of material onto the growth substrate. This approach requires applications of the fundamental knowledge of surface chemistry and reactivity of small molecules to effectively block deposition on nongrowth substrates and to not substantially affect deposition on the growth surface. Thus, many of the concepts of classical surface chemistry that had been developed over several decades can be applied to design such small molecule inhibitors. This article will outline the approaches for such design. This is especially important now, since the ever-increasing number of applications of this concept still rely on trial-and-error approaches in selecting SMI. At the same time, there is a very substantial breadth of surface chemical reactivity analysis that can be put to use in this process that will relate the effectiveness of a potential SMI on any combination of surfaces with the following: selectivity; chemical stability of a molecule on a specific surface; volatility; steric hindrance, geometry, packing, and precursor of choice for material deposition; strength of adsorption as detailed by interdisplacement to determine the most stable SMI; fast attachment reaction kinetics; and minimal number of various binding modes. The down-selection of the SMI from the list of chemicals that satisfy the preliminary criteria will be decided based on optimal combinations of these requirements. Although the specifics of SMI selection are always affected by the complexity of the overall process and will depend drastically on the materials and devices that are or will be needed, this roadmap will assist in choosing the potential effective SMIs based on quite an exhaustive set of “SMI families” in connection with general types of target surfaces.