Current surface modification chemistry of silicon nitride (Si3N4) in the fabrication of micro/nano systems (MEMS/NEMS) mainly relies on multistep chemical processes, essentially consisting of a surface pretreatment and a challenging silanization procedure. Although direct modification of Si3N4 surface has rarely been reported in the literature, here a simple surface functionalization strategy using diazonium chemistry in open air and at room temperature, which provides a practical solution to directly attach aminophenyl groups to pristine silicon nitride without altering its intrinsic properties, is described. These strongly grafted amine‐terminated groups are easily activated to become nuclei for initializing electroless nickel plating (autocatalytic nickel deposition). This electroless nickel plating of silicon nitride while avoiding the multiplicity and complexity of the process steps is ideal for its integration into a typical MEMS/NEMS process flow. In a possible integration scheme, due to its suitable properties, this nickel film serves as a conducting seed layer for the electrolytic deposition of copper to fill the microdevices, thereby avoids the use of typically employed expensive vacuum processes.
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