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Soft-nanoimprint lithography is a high-throughput and cost-effective lithographic technique with high resolution and low pressure, of which the crucial component is the mold. We demonstrate a method to fabricate hybrid soft-nanoimprint mold in benign ambient based on UV-curable thiol–ene polymer. Because of the special photopolymerization mechanism via “click chemistry”, thiol–ene can be cured completely at ambient conditions without inhabitation from oxygen or moisture. The mold can be fabricated in air not in vacuum or a nitrogen atmosphere to simplify the fabrication process and lower the cost. Based on this method, we fabricated a soft-nanoimprint hybrid mold in benign ambient, which is composed of rigid thiol–ene features with sub-60nm resolution on an elastic poly(dimethylsiloxane) (PDMS) substrate.