Current semiconductor manufacturing utilizes exposure wavelengths from 365 nm to 193 nm, and current research is centered on photoresist development for 157 nm. Our research group discovered the strong inhibition response in the fluorocarbon resins designed for use at 157 nm. We have been investigating dissolution inhibitors (DIs), some of which also serve as photoacid generators (PAGs), that strongly inhibit the dissolution of poly(2-(3,3,3-trifluoro-2-trifuoromethyl-2-hydroxypropyl) bicyclo[2.2.1]heptane-5-ene)(PNBHFA) (1) and the Asahi glass RS001 polymer (2). These inhibiting PAGs, in particular, result in the creation of 2-component resist systems consisting only of the resin polymer and the PAG-DI. This design enables greater ease of formulation, reduces the number of variables present in resist development, and offers improvements in sensitivity and line edge roughness. The synthetic approach has been to design transparent, inhibiting compounds for use at 157 nm. However, during our investigation of these compounds, we found that there is an inherent “backwards compatibility” for these PAGs and DIs at 193 nm, 248 nm and 365 nm. This has created the ability to effectively design dissolution inhibitors, photoactive or otherwise, that span virtually all of the wavelengths used in photolithographic processes today. Here we will present the design, development and imaging of modern dissolution inhibitors suitable for use in a wide range of photolithography technologies.
The focus of 157 nm lithographic research is shifting from materials research to process development. Poly (2-(3,3,3-trifluoro-2-trifuoromethyl-2-hydroxypropyl) bicyclo[2.2.1]heptane-5-ene) (PNBHFA) has received a great deal of attention as a possible base resin for 157 nm lithography. The Asahi Glass RS001 polymer, which was introduced at SPIE in 2002, has also shown promise as a 157 nm base resin due to its low absorbance. Partial protection of either polymer with an acid labile protecting group is a common design for functional photoresists. We previously reported the blending of the carbon monoxide copolymers with PNBHFA copolymers to achieve the critical number of protected sites for optimum imaging performance and contrast. Our group has since studied the use of the unprotected base resin with an additive monomeric dissolution inhibitors (DIs) and a photoacid generator (PAG) to form a three component resist. Surprisingly unprotected PNBHFA was discovered to have dissolution inhibition properties that are far superior to the dissolution inhibition properties of novolac. Several DIs were prepared and tested in PNBHFA to take advantage of the resins dissolution inhibition properties. We have also recently explored the performance of a two-component resist using PAGs that also function as DIs.