Journal
CHEMELECTROCHEM
Volume 2, Issue 5, Pages 664-671Publisher
WILEY-V C H VERLAG GMBH
DOI: 10.1002/celc.201402427
Keywords
additives; copper plating; electrodeposition; recrystallization; secondary ion mass spectrometry
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Funding
- Swiss National Science Foundation (SNSF)
- Marie-Heim-Vogtlin program of the SNSF
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The recrystallization behavior of Cu films electrodeposited under oscillatory conditions in the presence of plating additives was studied by means of secondary ion mass spectrometry (SIMS) and focused ion beam analysis. When combined with bis-(sodium-sulfopropyl)-disulfide (SPS), Imep levelers (polymerizates of imidazole and epichlorohydrin) show characteristic oscillations in the galvanostatic potential/time transient measurements. These are related to the periodic degradation and restoration of the active leveler ensemble at the interface. The leveler action relies on adduct formation between the Imep and MPS (mercaptopropane sulfonic acid)-stabilized Cu-I complexes that appear as intermediates of the copper deposition when SPS is present in the electrolyte. SIMS depth profiling proves that additives are incorporated into the growing film preferentially under transient conditions during the structural breakdown of the leveler ensemble and its subsequent restoration. In contrast, Cu films electrodeposited in the presence of a structurally intact Imep-Cu-I-MPS ensemble remain largely contamination free.
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