At the 32nm node, the most important issue for mass production in immersion lithography is defectivity control. Many methods have been studied to reduce post-exposure immersion defects. Although a topcoat process demonstrates good immersion defect prevention, a topcoat-less resist process is an attractive candidate for immersion lithography due to cost reduction from a simplified process. In this paper we took the innovative approach of chemically designing an internal self-assembling barrier material that creates a thin embedded layer which functions as a topcoat. Data will be presented on this novel self assembly concept, illustrating the control of leaching, contact angle and immersion defects. Several optimized process flows with non-topcoat resists were also studied to decrease the amount of immersion defects. This study was used to verify the capability of a topcoat-less immersion process to achieve the low-defectivity levels required for 32nm node production.