Enhanced Deposition Selectivity of High‑k Dielectrics by Vapor Dosing and Selective Removal of Phosphonic Acid Inhibitors

Area-selective atomic layer deposition (AS-ALD), which provides a bottom-up nanofabrication method with atomic-scale precision, has attracted a great deal of attention as a means to alleviate the problems associated with conventional top-down patterning. In this study, we report a methodology for achieving selective deposition of high-k dielectrics by surface modification through vapor-phase functionalization of octadecylphosphonic acid (ODPA) inhibitor molecules accompanied by post-surface treatment. A comparative evaluation of deposition selectivity of ZrO₂ thin films deposited with the O₂ and O₃ reactants was performed on SiO₂, TiN, and W substrates, and we confirmed that high enough deposition selectivity over 10 nm can be achieved even after 200 cycles of ALD with the O₂ reactant. Subsequently, the electrical properties of ZrO₂ films deposited with O₂ and O₃ reactants were investigated with and without post-deposition treatment. We successfully demonstrated that high-quality ZrO₂ thin films with high dielectric constants and stable antiferroelectric properties can be produced by subjecting the films to ozone, which can eliminate carbon impurities within the films. We believe that this work provides a new strategy to achieve highly selective deposition for AS-ALD of dielectric on dielectric (DoD) applications toward upcoming bottom-up nanofabrication.