The structure and as such the properties of alkanethiolate self-assembled monolayers (SAMs) on metal surfaces depend on the surface structure, thiolate coverage and chain length. The chain length dependence of alkanethiolate phases on Au surfaces is extensively documented. Much less insight exists for alkanethiolate SAMs on Cu surfaces, despite the relevance for area-selective deposition (ASD) applications. This work therefore studies the phase behavior of alkanethiolates on Cu through density functional theory (DFT) modelling. Short chain thiolates (C1,2) display no phase behavior and their saturation coverage is determined by steric hindrance. Longer thiolates (C6,12)show distinct lying-down and standing-up phases. The substrate-adsorbate interactions become weaker with increasing thiolate content, but still dominate in the standing-up phase at the saturation content of 5.1•10 14 thiolates•cm -2 . This is in contrast to Au [100] surfaces, where intermolecular interactions dominate at the saturation content, which is slightly higher than that on Cu[100]. The saturation coverage seems to be determined primarily by steric hindrance, which in turn will depend on the lattice parameter of the surface. We conclude that insights for alkanethiolate SAMs on Au cannot necessarily be transferred to Cu.

Area‐selective deposition (ASD) is a promising bottom‐up approach for fabricating nanoelectronic devices. However, a challenge is to prevent the undesired growth of nanoparticles in the nongrowth area. This work uses kinetic Monte Carlo (KMC) methods to investigate the defectivity in ruthenium ASD by (ethylbenzyl)(1‐ethyl‐1,4‐cyclohexadienyl)Ru/O2 (EBECHRu) atomic layer deposition (ALD) in line‐space nanopatterns with different dimensions. Ru ASD is governed by adsorption as well as diffusion. The defectivity depends on the pattern dimensions, as nanoparticles can diffuse and reach the interface with the growth area where they aggregate. For linewidths of 50 nm and smaller, all Ru adspecies are captured at the growth interface before growth by precursor adsorption is catalyzed. The synergetic effect of diffusion and size‐dependent reactivity reduces defectivity below 1010 Ru atoms cm−2 for at least 1000 ALD cycles. This is more than 1000 times lower than for patterns with a linewidth of 200 nm and larger, where the Ru content decreases significantly only near the interface with the growth surface. The predicted depletion zone is confirmed by experiments in nanoscale line‐space patterns. Overall, this mechanism results in smaller and fewer Ru nanoparticles for smaller patterns, facilitating the development of passivation‐deposition‐etch ASD processes for nanoelectronic device fabrication.

Area-selective atomic layer deposition (AS-ALD) is a coveted method for the fabrication of next-generation nano-electronic devices, as it can complement lithography and improve alignment through atomic scale control. Selective reactions of small molecule inhibitors (SMIs) can be used to deactivate growth on specific surface areas and as such enable AS-ALD. To investigate new applications of ASD, we need insight into the reactions of SMIs with a broad range of technology relevant materials. This paper investigates the reactions of aminosilane SMIs with a broad range of oxide surfaces and the impact on subsequent atomic layer deposition (ALD). We compare the reactions of two aminosilane SMIs, namely, dimethylamino-trimethylsilane (DMA-TMS) and hexamethyldisilazane (HMDS), with a hydroxylated SiO2 surface and the impact on subsequent ALD processes. The DMA-TMS reaction saturates faster than the HMDS reaction and forms a dense trimethylsilyl (TMS) layer with a higher TMS surface concentration. The higher TMS surface concentration yields better inhibition and higher selectivity during subsequent TiO2 ALD. We show that a wide range of surfaces, i.e., MgO, HfO2, ZrO2, Al2O3, TiO2 (TiN/TiOx), SiO2, SnO2, MoOx, and WO3 remain reactive after DMA-TMS exposure for conditions where SiO2 is passivated, indicating that DMA-TMS can enable AS-ALD on these surfaces with respect to SiO2. On these surfaces, DMA-TMS forms residual TMS and/or SiOxCyHz surface species that do not markedly inhibit ALD but may affect interface purity. Surfaces with lower, similar, and higher surface acidity than SiO2 all show less reactivity toward DMA-TMS, suggesting that surface acidity is not the only factor affecting the substrate-inhibitor interaction. Our study also compares a hybrid inorganic-organic SnOxCyHz and inorganic SnO2 material in view of their relevance as resist for extreme ultraviolet lithography. DMA-TMS can enable selective infiltration in SnOxCyHz, as opposed to selective deposition on SnO2, indicating tunable reactivity by bulk and surface composition. These insights into the reactivity of aminosilane SMIs may aid the design of new area-selective deposition processes, broaden the material space, and enable new applications.