Abstract
Area-selective atomic layer deposition (AS-ALD) has focused on controlling the promotion or blocking of precursor molecules on "heterogeneous" surfaces comprising different materials. This study proposes a new concept of AS-ALD on "homogeneous" surfaces comprising a single material. In this work, a homogeneous ZrO(2) substrate is selectively fluorinated using sulfur hexafluoride (SF(6)) gas. The SF(6) decomposes and incorporates into oxygen vacancies in ZrO(2), forming F-terminated surface at grain boundaries (GBs). In the following step, the remaining hydroxyl-terminated ZrO(2) areas are blocked by a cyclopentadienyl ligand to prevent aluminum precursor adsorption. Density functional theory and Monte Carlo simulations show that selectively passivated GBs of ZrO(2) lead to the selective adsorption of ZrCp(NMe(2))(3) inhibitors. Selective growth of Al(2)O(3) along GBs of ZrO(2) is observed by elemental mapping from transmission electron microscopy. Finally, GB-selective Al(2)O(3) increases overalldielectric constant by 15.5% in ZrO(2)/Al(2)O(3)/ZrO(2) stacks with no increase in leakage currents, showing that the GB-selective Al(2)O(3) incorporation suffices to passivate leakage paths through ZrO(2) GBs. These findings provide fundamental guidelines for performing AS-ALD on homogeneous surfaces and highlight the potential of this approach for applications in next-generation electronic devices.