with modification of surface characteristics, which allows a desired film to be deposited on one region of pre-patterned surfaces (i.e., growth areas) while simultaneously inhibiting deposition in adjacent regions (i.e., non-growth areas). [3,[7][8][9][10] One of the most common strategies for the successful implementation of AS-ALD is to locally deactivate non-growth areas with self-assembled monolayers (SAMs) as inhibitor molecules. [11][12][13][14][15][16][17] In other words, surface modification with such alkylating agents is the most important prerequisite in that the subsequent ALD process operates with a strong dependence of the surface character in the employed substrates by virtue of a surface-reaction-controlled regime with an alternating exposure of precursor and co-reactant molecules. [4][5][6]18] Despite many efforts in successful AS-ALD methods using SAMs, there remain several challenges for practical implementation of selective deposition with SAMs in an industry-compatible process. First, due to a lack of volatility, monolayeric formation of uniform SAMs requires an exceedingly long coating time involving immersion into SAMcontaining solutions for several hours to a few days, depending on the type of SAMs and employed substrates. [13,[19][20][21][22][23][24] In addition, their blocking capability against the subsequent ALD process relies on alkyl chain lengths in the backbone of SAMs, such that using SAMs with alkyl chain lengths greater than 12 units of carbon can provide high enough blockage by virtue of strong van der Waals interaction between adjacent SAMs. [16] However, when it comes to the formation of such bulky SAMs across complex 3D nanostructures with regions of high curvature, the presence of their steric hindrance appears to be a critically limiting factor to confer deposition selectivity, indicative of incompatibility with advanced 3D nanofabrication. [25] To overcome the above-indicated limitations, many attempts have been made to enable facile and efficient surface modification through vapor-phase functionalization of small inhibitor molecules on non-growth areas. [1,4,7,17,26] Among them, surface alteration with vapor dosing of such short-chain aminosilanes showed promise toward rendering much smaller surface alkylating agents with short exposure times, making it more suitable for integration of AS-ALD in the complex and 3D nanostructures. However, their blocking ability was found to be limited to very thin films in comparison with long-chain SAMs due to the relatively limited van der Waals interactions between short alkyl Area-selective atomic layer deposition (AS-ALD) has enormous potential for selective formation of thin films in a bottom-up additive fashion on predefined areas. Despite significant efforts in a number of AS-ALD processes using bulky self-assembled monolayers (SAMs) with long alkyl chains as inhibitor molecules on non-growth areas, there is increasing interest in achieving selective deposition compatible with complex 3D structures with smaller technology nodes in...

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