Superconformal Au deposition is demonstrated in a
Na
3
Au(SO
3
)
2 +
Na
2
SO
3
electrolyte using Bi species to catalyze the reduction of
Au(SO
3
)
2
3−
. Micromolar additions of
Bi
3+
to the sulfite-based electrolyte accelerate the reduction of
Au(SO
3
)
2
3−
as shown by hysteretic
voltammetry and rising chronoamperometric transients. Superconformal feature
filling is observed over a defined range of Bi
3+
concentration,
potential and hydrodynamics. Over a more limited parameter range, approximately
−0.9 V to −0.95 V, void-free, bottom-up filling of Damascene
trenches is achieved. Furthermore, in the presence of significant convection the
bottom-up filling is accompanied by passivation of the free surface. Bottom-up
feature filling is characterized by a counterintuitive dependence of the free
surface reactivity on the available flux of the Bi
3+
accelerator
species suggestive of an unusual coupling between hydrodynamic transport, shear
and interfacial chemistry.