Polymer-bound photobase generators and photoacid generators for pitch division lithography

The semiconductor industry is pursuing several process options that provide pathways to printing images smaller than the theoretical resolution limit of 193 nm projection scanners. These processes include double patterning, side wall deposition and pitch division. Pitch doubling lithography (PDL), the achievement of pitch division by addition of a photobase generator (PBG) to typical 193 nm resist formulations was recently presented. 1 Controlling the net acid concentration as a function of dose by incorporating both a photoacid generator (PAG) and a PBG in the resist formulation imparts a resist dissolution rate response modulation at twice the frequency of the aerial image. Simulation and patterning of 45 nm half pitch L/S patterns produced using a 90 nm half pitch mask were reported. 2 Pitch division was achieved, but the line edge roughness of the resulting images did not meet the current standard. To reduce line edge roughness, polymer bound PBGs and polymer bound PAGs were investigated in the PDL resist formulations. The synthesis, purification, analysis, and functional performance of various polymers containing PBG or PAG monomers are described herein. Both polymer bound PBG with monomeric PAG and polymer bound PAG with monomeric PBG showed a PDL response. The performance of the polymer bound formulations is compared to the same formulations with small molecule analogs of PAG and PBG.