Competitive Adsorption as a Route to Area-Selective Deposition

In this work, we have explored the use of a third species during chemical vapor deposition (CVD) to direct thin-film growth to occur exclusively on one surface in the presence of another. Using a combination of density functional theory (DFT) calculations and experiments, including in situ surface analysis, we have examined the use of 4-octyne as a coadsorbate in the CVD of ZrO₂ thin films on SiO₂ and Cu surfaces. At sufficiently high partial pressures of the coadsorbate and sufficiently low substrate temperatures, we find that 4-octyne can effectively compete for adsorption sites, blocking chemisorption of the thin-film precursor, Zr[N(CH₃C₂H₅)]₄, and preventing growth on Cu, while leaving growth unimpeded on SiO₂. The selective dielectric-on-dielectric (DoD) process developed herein is fast, totally vapor phase, and does not negatively alter the composition or morphology of the deposited thin film. We argue that this approach to area-selective deposition (ASD) should be widely applicable, provided that suitable candidates for preferential binding can be identified.