Nanostructured Mixed Layers of Organic Materials Obtained by Nanosphere Lithography and Electrochemical Reduction of Aryldiazonium Salts.

In this work, we have combined nanosphere lithography with electrochemical reduction of aryldiazonium salts to elaborate nanostructured mixed layers of organic materials. The strategy consists first in the deposition of a close-packed hexagonal monolayer of microbeads used as a mask for the electroreduction of a first aryldiazonium salt. After removing the beads, an ultrathin organic layer with holes remains. Then, a second aryldiazonium salt is electrochemically reduced selectively inside the holes. The relative thickness of the two deposited materials can be changed, leading to mixed layers of different topographies. Moreover, using diazoniums with complementary redox properties, a modified bifunctional electrode acting as a filter for electron transfer with a low potential gap has been obtained. Such layers are similar to low-band-gap organic semiconductors that can be easily n or p doped. Despite this analogy, the oxidation and reduction of redox probes in solution on such nanostructured surfaces occur on completely separated areas of the mixed layer.