Negative tone molecular resists using cationic polymerization: Comparison of epoxide and oxetane functional groups

Two molecular resists with a common molecular glass core were synthesized and characterized to compare the differences between epoxide (oxirane) and oxetane functional groups for use in high resolution negative tone molecular resists. Both resists are able to obtain at least 50nm half-pitch at a sensitivity of 75μC∕cm2 under 100keV electron-beam lithography. Due to differences in the kinetics of the cationic polymerization of epoxides as compared to oxetanes, the epoxide functionalized resist (2-Ep) was able to obtain sub-25-nm half-pitch resolution with good line edge roughness (LER) of 2.9nm (3σ) while the oxetane resist (2-Ox) was limited to 50nm half-pitch resolution and exhibited higher LER (3σ) of 10.0nm. The polymerization of the oxetane functional group has slow initiation and fast propagation which leads to reduced performance in 2-Ox as compared to 2-Ep. While oxetane functionalized molecular resists can obtain reasonably good imaging performance, epoxide functional groups show more promise for use in next generation negative tone resists that have a good combination of resolution, sensitivity, and LER.