Direct observation of the diffusion behavior of an electrodeposition additive in through-silicon via using in situ surface enhanced Raman spectroscopy

In this work, the behavior of an additive designed to aid electrodeposition in through-silicon via (TSV) structures is monitored directly using surface enhanced Raman spectroscopy (SERS). A horizontal via structure with a transparent ceiling (corresponding to the side wall of the TSV) was prepared, which allowed the probe laser to reach the bottom of the structure (corresponding to the opposite side of the TSV wall). Au nanoparticles of size ~5 nm deposited on the bottom of the structure produced a SERS effect and enhanced the Raman signals of chemical species migrating nearby. The diffusion behavior of the additive inside the via structure could be monitored with high sensitivity by detecting these enhanced signals. As a case study, this direct measurement method was successfully used to follow the diffusion of a small amount of Janus Green B, a common additive for Cu electrodeposition. The diffusion coefficient of the additive determined by these measurements turned out to be different to that estimated electrochemically on flat electrodes. One of the advantages of our direct measurement setup is the ability to exclude the undesirable environmental changes that often occur in electrochemical measurements.