A series of five star-shaped teroligomers consisting of a saccharose core, and arms, composed of α-gamma butyrolactone methacrylate (GBLMA), methyl adamantyl methacrylate (MAMA) and hydroxyl adamantyl methacrylate (HAMA) with defined arm length and number of arms were prepared via the core-first atom transfer radical polymerization (ATRP) route. The saccharose core was modified with ATRP initiating sites and non-reactive sites, enabling the synthesis of star polymers with a smaller arm number but identical core. Star teroligomers were synthesized with narrow molecular weight distributions with low polydispersity indices (PDIs < 1.1) showing negligible side reactions only at higher conversions of Xp > 50%. The absence of side reaction and the precise achievement of the target molecular weight indicated excellent control over the reaction. A selected star-shaped teroligomer was investigated for the first time as a photoresist material. The delicate conditions of the lithographic process were optimized by a combinatorial approach. The obtained low line edge and line width roughness of the observed pattern demonstrate the potential of the star architecture for this application.
