Slurry Chemistry Effects On Copper Chemical Mechanical Planarization (2004)

Chemical-mechanical Planarization (CMP) has emerged as one of the fastest-growing processes in the semiconductor manufacturing industry, and it is expected to show equally explosive growth in the future (Braun, 2001). The development of CMP has been fueled by the introduction of copper interconnects in microelectronic devices. Other novel applications of CMP include the fabrications of microelectromechanical systems (MEMS), advanced displays, three dimensional systems, and so on (Evans, 2002). CMP is expected to play a key role in the next-generation micro- and nanofabrication technologies (Singh, et al., 2002). Despite the rapid increase in CMP applications, the fundamental understanding of the CMP process has been lacking, particularly the understanding of the wafer-slurry-pad interactions that occur during the CMP process. Novel applications of CMP are expected to expand to materials that are complex chemically and fragile mechanically. Thus, fundamental understanding and improvement of slurry design for CMP is the key to the development of sophisticated next-generation CMP processes. Slurry performance for CMP can be determined by several output parameters including removal rate, global planarity, surface topography, and surface defectivity. To achieve global planarity, it is essential to form a very thin passivating surface layer ( < 2 nm) that is subsequently removed by the mechanical component of the slurry (Kaufman et al., 1991) or by combined chemo-mechanical effects (Tamboli, 2000). Chemical additives like hydrogen peroxide (H2O2), potassium ferricyanide, and ferric chloride are added to slurries as oxidizers in order to form a desirable surface layer. Other chemical additives such as inhibitors (e.g. benzotriazole) and complexing agents (e.g. ammonia) are added to the copper slurry in order to modify the oxide layer. That the removal rate of the thin surface layer is greater at the highest regions of the wafer surface than at the lowest regions leads to surface planarity. In this study, various complexing agents and inhibitors are combined to form slurry chemistry for copper CMP processing in H2O2 based slurries at pH values ranging from 2 to 10. Two complexing agents (glycine and Ethylenediamine) and one inhibitor (3-amino-1, 2, 4-triazole) were selected as slurry constituents for detailed chemical synergistic effect study because they showed good materials removal and surface planarity performances. To understand the fundamental mechanisms involved in copper CMP process with the afore-mentioned slurry chemical formations, various techniques, such as electrochemical testing techniques (including potentiodynamic polarization and electrochemical impedance spectroscopy), x-ray photoelectron spectroscopy (XPS), atomic force microscopy (AFM), and scanning electron microscopy (SEM), were applied. As a result, guidelines for optimized slurry chemical formulation were arrived at and the possible mechanisms of surface-chemical-abrasive interactions were determined. From applications point of view, this study serves as a guide for further investigations in pursuing highly effective slurry formulations for copper/low-k interconnect applications.