Methods for fabricating an IC structure by applying self-assembled monolayers (SAMs) are disclosed. An example IC structure includes a stack of three metallization layers provided over a support structure, where the first metallization layer includes a bottom metal line, the third metallization layer includes a top metal line, and the second metallization layer includes a via coupled between the bottom metal line and the top metal line, where via's sidewalls are enclosed by a first dielectric material. Application of one or more SAMs results in at least a portion of the via's sidewalls being lined with a second dielectric material so that the second dielectric material is between the first dielectric material and an electrically conductive material of the via, where the dielectric constant of the second dielectric material is higher than that of the first dielectric material and lower than about 6.