In-situ cleaning and passivation of oxidized Cu surfaces by alkanethiols and its application to wire bonding

The treatment of oxidized Cu surfaces using an alkanethiol as a reducing agent has been investigated. Exposure to a dilute solution of 1-decanethiol resulted in the complete removal and/or conversion of CuO and subsequent formation of a passivating thiolate film, a so-called self-assembled monolayer (SAM), on the underlying Cu/Cu₂O surface as evidenced by x-ray photoelectron spectroscopy (XPS) analysis. Morphological changes, monitored by scanning electron microscopy (SEM) and atomic force microscopy (AFM), revealed transformation of the rough, porous CuO layer into a comparatively smooth Cu/Cu₂O surface. Experiments performed on integrated circuit back-end-of-line (BEOL) die structures, comprising Cu/SiO₂ bond pads used as substrates for Cu wire bonding, demonstrate the potential application of a thiol-based in-situ cleaning-passivation procedure in microelectronics.