Structural design of a new class of acetal polymer for DUV resists

Physical and lithographic properties of functionalized acetal- based polymers, newly designed bulky acetals, were investigated for the use of KrF DUV resist. The key structural design was to incorporate some functional groups into the acetal moieties in the polymers through an ether or ester linkage. The polymers were synthesized by reacting poly p- hydroxy styrene (PHS) with variety of functionalized vinyl ethers that were prepared with substitution reaction of chloroethyl vinyl ether. By selecting large moieties in size for the functional group, the polymers showed good lithographic performance even with a low level of the acetal blocking. This was advantageous for minimizing the defects that could generally be formed in image development and also for improving dry etch resistance of the resist. The ester- linked polymers showed a high dissolution discrimination which could be accounted for with dissolution inhibition induced by a molecular interaction of the ester group with photo acid generator (PAG) in the resist composition. A new class of acetal polymers having additional another acid-decomposable group in the functional group is also proposed for achieving a further improvement in lithographic property.