Thermal Atomic Layer Etching of Nickel Using Sequential Chlorination and Ligand-Addition Reactions

Abstract

The thermal atomic layer etching (ALE) of nickel was demonstrated using sequential chlorination and ligand-addition reactions. Nickel chlorination was achieved using SO2Cl2 (sulfuryl chloride) as the chlorine reactant. PMe3 (trimethylphosphine) was employed as the ligand-addition reactant. Sequential exposures of SO2Cl2 and PMe3 led to Ni thermal ALE. This procedure was inspired by the covalent bond classification (CBC) method that categorizes the most common compounds of various metals. Based on the CBC method, the surface reactions during thermal Ni ALE were performed to form NiX2L2 products, where Cl is the X ligand and PMe3 is the L ligand. Using this strategy, thermal Ni ALE was observed at temperatures from 75–200 °C. The etch rates were determined from in situ quartz crystal microbalance (QCM) measurements. The average etch rates determined from the mass changes were 0.14 ± 0.13, 0.57 ± 0.36, 0.67 ± 0.45, 1.30 ± 0.68, and 3.07 ± 1.56 Å/cycle for the temperatures 75, 100, 125, 150, and 175 °C, respectively. The QCM investigations revealed that there was a mass increase on every SO2Cl2 exposure and a mass loss on every PMe3 exposure, resulting in a net mass loss. The amount of chlorination for a given SO2Cl2 exposure increased with increasing temperature. The amount of mass lost on each PMe3 exposure also increased with increasing temperature. The etch rates were also confirmed using ex situ X-ray reflectivity measurements on Ni films on silicon wafers. The etch rates varied from 0.39 ± 0.10 Å/cycle at 125 °C to 2.16 ± 0.47 Å/cycle at 200 °C. Mass spectrometry analysis revealed that the volatile etch product was NiCl2(PMe3)2 as expected from the CBC method. In addition, scanning electron microscopy revealed that the nickel surface morphology had negligible changes after ALE. Atomic force microscopy analysis showed that thin nickel films remained smooth during initial etching and may experience some slight roughening with progressive etching. Using the CBC method to create novel thermal ALE procedures can be generalized for the thermal ALE of many different metals.