The ability to reverse the inherent tendency of noble metals to grow in an uncontrolled three-dimensional (3D) fashion on weakly interacting substrates, including two-dimensional (2D) materials and oxides, is essential for the fabrication of high-quality multifunctional metal contacts in key enabling devices. In this study, we show that this can be effectively achieved by deploying nitrogen (N2) gas with high temporal precision during magnetron sputtering of nanoscale silver (Ag) islands and layers on silicon dioxide (SiO2) substrates. We employ real-time in situ film growth monitoring using spectroscopic ellipsometry, along with optical modeling in the framework of the finite-difference time-domain method, and establish that localized surface plasmon resonance (LSPR) from nanoscale Ag islands can be used to gauge the evolution of surface morphology of discontinuous layers up to a SiO2 substrate area coverage of ∼70%. Such analysis, in combination with data on the evolution of room-temperature resistivity of electrically conductive layers, reveals that presence of N2 in the sputtering gas atmosphere throughout all film-formation stages: (i) promotes 2D growth and smooth film surfaces and (ii) leads to an increase of the continuous-layer electrical resistivity by ∼30% compared to Ag films grown in a pure argon (Ar) ambient atmosphere. Detailed ex situ nanoscale structural analyses suggest that N2 favors 2D morphology by suppressing island coalescence rates during initial growth stages, while it causes interruption of local epitaxial growth on Ag crystals. Using these insights, we deposit Ag layers by deploying N2 selectively, either during the early precoalescence growth stages or after coalescence completion. We show that early N2 deployment leads to 2D morphology without affecting the Ag-layer resistivity, while postcoalescence introduction of N2 in the gas atmosphere further promotes formation of three-dimensional (3D) nanostructures and roughness at the film growth front. In a broader context this study generates knowledge that is relevant for the development of (i) single-step growth manipulation strategies based on selective deployment of surfactant species and (ii) real-time methodologies for tracking film and nanostructure morphological evolution using LSPR.

Manipulation of thin silver film growth on weakly-interacting silicon dioxide substrates using oxygen as a surfactant Running title: Manipulation of thin silver film growth on weakly-interacting silicon dioxide substrates using oxygen as a surfactant