Precise Control of Nanoscale Cu Etching via Gas-Phase Oxidation and Chemical Complexation

We present a cyclic process for selective and anisotropic atomic layer etching of copper: an oxygen plasma modulates the depth and directionality of the oxidized layer, while formic acid vapor selectively removes the copper oxide scale from the metallic copper. Via density functional theory, with finite temperature and pressure free energy corrections, we evaluate the feasibility of formation of gas-phase Cu­(II) and Cu­(I) complexes with formate, water, formic acid, and combinations thereof as ligands. These complexes result from the neutralization reaction between copper oxide (CuO and Cu2O) and formic acid, with and without water. We identified and evaluated the formation free energies of formato, formic acid, aquahydroxo, and aquaformato complexes of Cu­(II) and Cu­(I). Under relevant experimental pressures, we find the water-free dimeric tetra­(μ-formato)­dicopper­(II) “paddlewheel” complex (Cu2(HCOO)4) to be the most favorable etching product, with its formation reaching equilibrium conditions from CuO. The most likely precursor for the dimer is the diformatodi­(formic acid)­copper­(II) monomer, which favorably dimerizes under the same water-lean condition at which the dimer persists. Stabilization of gas-phase Cu (oxide) derivatives thus can be achieved through complexation, enabling gas-phase etching of Cu. This work provides complementary experimental and theoretical studies that illuminate the nature of highly controlled etching with formic acid of nanoscopic CuO(s) layers covering Cu nanoarchitectures, which is relevant for the fabrication of next-generation integrated circuits.