Oscillatory
electrodeposition reactions have been utilized to create
nanostructured materials under the microscale and nanoscale. This
alternative method of synthesis, when compared to the traditional
step-by-step synthesis procedure, takes advantage of the self-organizing
processes that do not require any external control or template-based
support, resulting in materials with higher complexity in terms of
structure and composition. Nanolayers made of Cu and semiconductor
composites, such as Cu/Cu2O, can be finely tuned by controlling
ordinary period-one oscillations in the cathodic deposition. As the
reaction media is alkaline, a complexing agent is commonly added in
the solution to prevent the precipitation of the copper ions as hydroxides.
Lactate and tartrate molecules are two α-hydroxy carboxylate
organic ligands extensively used for this aim. Although some studies
have shown the electrochemical synthesis of Cu/Cu2O nanolayers,
no grounded discussion about the influence of the chemical nature
of the ligands on the oscillatory reaction has been investigated so
far. Here, we provide a well-detailed and rigorous study of the effect
of both ligands in the electrodeposition of Cu/Cu2O under
galvanostatic control, accurately mapping differences in the oscillation
period and amplitude. On the basis of recent advances on the understanding
of the copper complex structures, we attributed a distorted tetrahedral
structure with four monodentate lactate ligands linked to the Cu2+ central ion ([Cu(Lac)4]2–)
and a distorted square-planar coordination of the tartrate’s
deprotonated alkoxide groups, forming a chelate ([Cu(TartH–2)2]6–), as the species that have a buffering
effect on the oscillatory mechanism and, consequently, can control
the extension of the oscillation period and amplitude. In this matter,
the tartrate complex should have a higher buffering capacity to prolong
the period and decrease the amplitude. More importantly, we unequivocally
show that a surface blocking effect due to the adsorption reactions
cannot be neglected in the mechanism description. The adsorption of
the tartrate anions and its complexes has, also as an outcome, period
enlargement and amplitude shrinkage, as compared to that of the lactate.
Hence, both mechanisms seem to operate in the adjustment of the dynamic
characteristics of the oscillatory electrodeposition of Cu/Cu2O.