RESUMO
This work demonstrates void-free Cu filling of millimeter size Through Silicon Vias (mm-TSV) in an acid copper sulfate electrolyte using a combination of a poloxamine suppressor and chloride, analogous to previous work filling TSV that were an order of magnitude smaller in size. For high chloride concentration (i.e., 1 mmol/L) bottom-up deposition is demonstrated with the growth front being convex in shape. Instabilities in filling profile arise as the growth front approaches the free-surface due to coupling with electrolyte non-uniform hydrodynamics. The reentrant notches at the bottom of the TSVs caused by intentional over-etching during fabrication negatively impact the filling results. In contrast, deposition from low chloride electrolytes (i.e., 80 µmol/L) proceeds with a passive-active transition on the via sidewalls. For a given applied potential the location of the transition is fixed in time and the growth front is concave in nature reflecting the gradient in chloride surface coverage. Application of a suitable potential wave form enables the location of the sidewall transition to be systematically advanced thereby giving rise to void-free filling of the TSV.
RESUMO
Gold deposition on rotating disk electrodes, Bi3+ adsorption on planar Au films and superconformal Au filling of trenches up to 45 µm deep are examined in Bi3+-containing Na3Au(SO3)2 electrolytes with pH between 9.5 and 11.5. Higher pH is found to increase the potential-dependent rate of Bi3+ adsorption on planar Au surfaces, shortening the incubation period that precedes active Au deposition on planar surfaces and bottom-up filling in patterned features. Decreased contact angles between the Au seeded sidewalls and bottom-up growth front also suggest improved wetting. The bottom-up filling dynamic in trenches is, however, lost at pH 11.5. The impact of Au concentration, 80 mmol/L versus 160 mmol/L Na3Au(SO3)2, on bottom-up filling is examined in trenches up to ≈ 210 µm deep with aspect ratio of depth/width ≈ 30. The microstructures of void-free, bottom-up filled trench arrays used as X-ray diffraction gratings are characterized by scanning electron microscopy (SEM) and Electron Backscatter Diffraction (EBSD), revealing marked spatial variation of the grain size and orientation within the filled features.
RESUMO
An electrodeposition process for void-free bottom-up filling of sub-millimeter scale through silicon vias (TSVs) with Cu is detailed. The 600 µm deep and nominally 125 µm diameter metallized vias were filled with Cu in less than 7 hours under potentiostatic control. The electrolyte is comprised of 1.25 mol/L CuSO4 -0.25 mol/L CH3SO3H with polyether and halide additions that selectively suppress metal deposition on the free surface and side walls. A brief qualitative discussion of the procedures used to identify and optimize the bottom-up void-free feature filling is presented.