Backbone Degradable Poly(aryl acetal) Photoresist Polymers: Synthesis, Acid Sensitivity, and Extreme Ultraviolet Lithography Performance

Abstract

A new class of acid labile poly(aryl acetal) polymers has been developed that can be used in photoresist formulations for next-generation microlithography techniques including extreme ultraviolet (EUV) or electron beam lithography. Example polymers have been synthesized by an optimized Suzuki polycondensation protocol. They are soluble in common photoresist solvents but are insoluble in water or aqueous bases that are used to develop positive photoresists. The structural design includes further elements that are aimed at improving photoresist resolution, stability, and etch resistance. Upon acid exposure, the acetal linkages are cleaved, and the polymers degrade into phenolic terphenyl fragments, which are readily soluble in a photoresist developer. Polymer degradation has been studied by NMR and LC-MS. Lithographic formulations have been developed and tested in line-and-space patterning experiments using EUV photolithography. Optimized resist formulations achieved 22 nm resolution with line width roughness values of 5.7 nm.