PHS with inert blocking groups for DUV negative resist

The synthesis, characterization, and lithographic evaluation of a polyhydroxystyrene (PHS) modified with isopropyloxycarbonate groups is described. The inert blocking group is attached to the hydroxyl sites on PHS resin to slow the dissolution rate and make the resin useful in resists designed for 0.263 N TMAH developers. A negative tone resist (CGR-IP) that is formulated with the modified polymer is compatible with the industry standard 0.263 N TMAH developer and is capable of resolving 0.22 micrometer L/S features and 0.14 micrometer isolated lines on a 0.50 NA imaging system. Reaction with PHS resin occurs primarily at the phenolic sites as shown by carbon-13 NMR and 10% protection is sufficient to lower the dissolution rate to an acceptable level so that there is less than 50 angstrom film loss in exposed areas. The blocking group described here is not acid labile and reaming intact after the resist film is baked at 150 degrees Celsius.