Zinc-Imidazolate Films as an All-Dry Resist Technology

Motivated by the drawbacks of solution phase processing, an all-dry resist formation process is presented that utilizes amorphous zinc-imidazolate (aZnMIm) films deposited by atomic/molecular layer deposition (ALD/MLD), patterned with electron beam lithography (EBL), and developed by novel low temperature (120 °C) gas phase etching using 1,1,1,5,5,5-hexafluoroacetylacetone (hfacH) to achieve well-resolved 22 nm lines with a pitch of 30 nm. The effects of electron beam irradiation on the chemical structure and hfacH etch resistance of aZnMIm films are investigated, and it is found that electron irradiation degrades the 2-methylimidazolate ligands and transforms aZnMIm into a more dense material that is resistant to etching by hfacH and has a C:N:Zn ratio effectively identical to that of unmodified aZnMIm. These findings showcase the potential for aZnMIm films to function in a dry resist technology. Sensitivity, contrast, and critical dimensions of the patterns are determined to be 37 mC cm⁻², 0.87, and 29 nm, respectively, for aZnMIm deposited on silicon substrates and patterned at 30 keV. This work introduces a new direction for solvent-free resist processing, offering the prospect of scalable, high-resolution patterning techniques for advanced semiconductor fabrication processes.