Superconformal Film Growth: From Smoothing Surfaces to Interconnect Technology.

ConspectusElectronics manufacturing involves Cu electrodeposition to form 3D circuitry of arbitrary complexity. This ranges from nanometer-wide interconnects between individual transistors to increasingly large multilevel intermediate and global scale on-chip wiring. At larger scale, similar technology is used to form micrometer-sized high aspect ratio through-silicon vias (TSV) that facilitate chip stacking and multilevel printed circuit board (PCB) metallization. Common to all of these applications is void-free Cu filling of lithographically defined trenches and vias. While line-of-sight physical vapor deposition processes cannot accomplish this feat, the combination of surfactants and electrochemical or chemical vapor deposition enables preferential metal deposition within recessed surface features known as superfilling. The same superconformal film growth processes account for the long-reported but poorly understood smoothing and brightening action provided by certain electroplating additives. Prototypical surfactant additives for superconformal Cu deposition from acid-based CuSO 4 electrolytes include a combination of halide, polyether suppressor, sulfonate-terminated disulfide, and/or thiol accelerator and possibly a N-bearing cationic leveler. Many competitive and coadsorption dynamics underlie functional operation of the additives. Upon immersion, Cu surfaces are rapidly covered by a saturated halide layer that makes the interface more hydrophobic, thereby supporting the formation of a polyether suppressor layer. Also, halide serves as a cosurfactant supporting the adsorption of amphiphilic molecular disulfide species on the surface while inhibiting copper sulfide formation and incorporation into the growing deposit. Furthermore, the dangling hydrophilic sulfonate end group of the accelerator enables activated metal deposition by hindering polyether suppressor assembly. A common thread in superconformal feature filling is additive-derived positive feedback of the metal deposition reaction within recessed or re-entrant regions. For submicrometer features or optically rough surfaces, area reduction that accompanies the motion of concave surface segments results in the most strongly bound adsorbates' enrichment, which for the suppressor-accelerator systems is the sulfonate-terminated disulfide accelerator species. The superfilling and smoothing process is quantitatively captured by the curvature-enhanced adsorbate coverage mechanism. For larger features, such as TSV, whose depths approach the thickness of the hydrodynamic boundary layer, significant compositional and electrical gradients couple with the metal deposition process to give a negative differential resistance and related nonlinear effects on morphological evolution. For certain suppressor-only electrolytes, remarkable bottom-up feature filling occurs where metal deposition disrupts inhibiting adsorbates at the bottom of the TSV or overruns the ability of the suppressor to form due to kinetic or transport limitations. Because the electrical response to changes in interface chemistry is more rapid than mass transport processes, deposition on planar substrates proceeds by bifurcation into passive and active zones, generating Turing patterns. On patterned substrates, active zone development is biased toward the most recessed regions. The distinction between packaging and on-chip metallization will be blurred as the dimensions of the former merge with those of early day on-chip 3D metallization.