Embodiments include package substrates and a method of forming the package substrates. A package substrate includes a self-assembled monolayer (SAM) layer over a first dielectric, where the SAM layer includes first end groups and second end groups. The second end groups may include a plurality of hydrophobic moieties. The package substrate also includes a conductive pad on the first dielectric, where the conductive pad has a bottom surface, a top surface, and a sidewall, and where the SAM layer surrounds and contacts a surface of the sidewall of the conductive pad. The hydrophobic moieties may include fluorinated moieties. The conductive pad includes a copper material, where the top surface of the conductive pad has a surface roughness that is approximately equal to a surface roughness of the as-plated copper material. The SAM layer may have a thickness that is approximately 0.1 nm to 20 nm.