Hollow
and Concave Nanoparticles via Preferential
Oxidation of the Core in Colloidal Core/Shell Nanocrystals
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Abstract
Hollow and concave nanocrystals find
applications in many fields,
and their fabrication can follow different possible mechanisms. We
report a new route to these nanostructures that exploits the oxidation
of Cu<sub>2–<i>x</i></sub>Se/Cu<sub>2–<i>x</i></sub>S core/shell nanocrystals with various etchants.
Even though the Cu<sub>2–<i>x</i></sub>Se core is
encased in a thick Cu<sub>2–<i>x</i></sub>S shell,
the initial effect of oxidation is the creation of a void in the core.
This is rationalized in terms of diffusion of Cu<sup>+</sup> ions
and electrons from the core to the shell (and from there to the solution).
Differently from the classical Kirkendall effect, which entails an
imbalance between in-diffusion and out-diffusion of two different
species across an interface, the present mechanism can be considered
as a limiting case of such effect and is triggered by the stronger
tendency of Cu<sub>2–<i>x</i></sub>Se over Cu<sub>2–<i>x</i></sub>S toward oxidation and by fast Cu<sup>+</sup> diffusion in copper chalcogenides. As the oxidation progresses,
expansion of the inner void erodes the entire Cu<sub>2–<i>x</i></sub>Se core, accompanied by etching and partial collapse
of the shell, yielding Cu<sub>2–<i>x</i></sub>S<sub><i>y</i></sub>Se<sub>1–<i>y</i></sub> concave
particles