THE SCHOOL OF MATERIALS SCIENCE AND ENGINEERING   GEORGIA INSTITUTE OF TECHNOLOGY   Under the provisions of the regulations for the degree   DOCTOR OF PHILOSOPHY   on Tuesday, October 31, 2017 12:00 PM in MaRC 431   will be held the   DISSERTATION DEFENSE   for   Timothy Huang   "Studies of Interfacial Adhesion and Copper Plating Chemistry for Metallization of Through-Package-Vias in Glass Interposers"   Committee Members:   Prof. Rao Tummala, Advisor, MSE Prof. Dong Qin, MSE Prof. Preet Singh, MSE Dr. Venkatesh Sundaram, ECE Dr. Rahul Manepalli, Intel Corporation   Abstract:   High quality copper plating in blind-vias and through-vias is crucial to achieve high electrical performance and reliability from the integrated circuit (IC) to the package substrate and printed wiring board (PWB). In efforts to meet the ever-increasing demand for improved system performance, recent trends in microelectronic packaging require finer Cu lines, micro vias, and fine-pitch Cu-filled through-package-vias (TPVs). Additionally, non-traditional package substrate materials such as glass are being investigated for their electrically insulating properties. These trends pose various material and process-related challenges in achieving high quality Cu metallization. Therefore, there is a strong need to investigate the fundamental aspects related to Cu adhesion and Cu plating chemistry. The objective of this research was to develop a fundamental understanding of various aspects related to copper deposition on glass for advanced package and interposer applications. This included investigating the following topics: 1) metallization and adhesion of Cu to ultra-thin glass substrates with small diameter, fine-pitch TPVs, 2) electrochemical characteristics of organic additives in electrolytic Cu plating, and 3) the mechanism of how organic additives in electrolytic Cu plating enable void-free Cu filling in vias. Various Cu to glass adhesion mechanisms were investigated. First, glass surface roughness was first studied as an approach to enable direct electroless Cu deposition. The feasibility was evaluated by determining the minimum required surface roughness and the interfacial failure mechanism. Then, a via-first process using a thin epoxy-based adhesion layer was developed. The process enabled electroless Cu deposition to ultra-thin glass substrates (100 µm) with small diameter (20 µm), fine pitch (40 µm) TPVs. Cu metallized glass substrates with TPVs passed thermomechanical reliability with strong adhesion after thermal cycle testing and highly accelerated stress testing. The impact of organic additives on electrolytic copper plating behavior was studied by electrochemical characterization. Using cyclic voltammetry and injection chronopotentiometry, the potential dependence and polarization kinetics of individual additives and combinations of additives were characterized. Their impact on Cu filling performance in blind-vias was investigated, and a mechanism was proposed to describe the additive interactions with the Cu via during plating. Finally, surface enhanced Raman spectroscopy (SERS) was used for in-situ observation of the chemical interactions between organic additives and the Cu surface during electroplating.