Click‐active surfaces patterned at 200 nm resolution are demonstrated using the dual functional polymeric film, poly(propargyl methacrylate) (PPMA). The commercially available monomer of propargyl methacrylate (PMA) is polymerized in a single step by initiated chemical vapor deposition (iCVD). FT‐IR and X‐ray photoelectron spectroscopy confirm retention of the click‐active acetylene functional group in the bulk and surface of the iCVD film, respectively. Treating substrates with silane coupling agents prior to deposition results in grafting of iCVD PPMA polymers onto various inorganic surfaces. This grafting technique provides the chemical and mechanical stability required for the PPMA layer to survive the subsequent wet chemical steps used for click functionalization. Successful attachment of an azido‐functionalized coumarin dye is demonstrated. Moreover, the PPMA film displays direct positive‐tone sensitivity to e‐beam irradiation, which enables e‐beam patterning without the use of a resist layer. Direct e‐beam exposure of the multifunctional PPMA iCVD layer results in a 200 nm pattern to which quantum dot nanoparticles are selectively conjugated on the substrates by click chemistry.

This work presents a detailed study of poly(neopentyl methacrylate-co-ethylene glycol diacrylate) [P(npMA-co-EGDA)] copolymer, which was selected for study from possible combination of 20 vinyl monomers and 4 divinyl crosslinkers as a candidate for sacrificial layer materials for the fabrication of air-gap structures. P(npMA-co-EGDA) was deposited onto substrates using an initiated chemical vapor deposition technique. Spectroscopic data showed the effective incorporation of both components in the copolymer and the retention of integrity of the repeating units. The onset temperature of decomposition of P(npMA-co-EGDA) and the removal percentage can be tuned between 290 and 350°C and 93 and 98%, respectively, by varying the composition of the copolymer. The removal rate of copolymer was calculated based on interferometry signal-time curve. For all copolymers, the activation energy was determined to be 162.7±8kJmol−1 . The products of thermal decomposition were monomers, rearranged small molecules, and low oligomers. The modulus and the hardness were in the range of 3.9–5.5 and 0.38–0.75GPa , respectively. Air-gap structures were constructed by patterning P(npMA-co-EGDA) with e-beam lithography, followed by capping with silica via plasma-enhanced chemical vapor deposition and thermal annealing at 360°C . The feature size of a 70nm air-gap structure was fabricated.