Plasmon-Based Free-Radical Photopolymerization: Effect of Diffusion on Nanolithography Processes
Plasmon-Based Free-Radical Photopolymerization: Effect of Diffusion on Nanolithography Processes
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DOI：
10.1021/ja201636y
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发表时间：
2011-07-13
影响因子：
15
通讯作者：
Soppera, Olivier
中科院分区：
文献类型：
--
作者：
Deeb, Claire;Ecoffet, Carole;Soppera, Olivier
本文探讨了受限和增强电磁场诱导纳米级光聚合的机理。单个银纳米粒子的表面等离子体偶极共振被用作光学近场源，以局部触发光聚合配方的反应。激光激发嵌入在配方中的纳米颗粒可再生地产生典型尺寸范围从2纳米到几十纳米的聚合物特征。我们确定了控制光聚合过程空间范围的理化参数和机理。我们发现染料的扩散是限制聚合反应的主要过程，而不是在微观尺度上用等效的化学系统观察到的。这种方法表明，基于等离子体的聚合可以实现真正的纳米级分辨率，也为在这种长度尺度上研究光化学提供了独特的机会。
This Article interrogates the mechanisms responsible for nanoscale photopolymerization induced by confined and enhanced electromagnetic fields. Surface plasmon dipolar resonance of individual Ag nanoparticles was used as an optical near-field source to locally trigger the reaction of a photopolymerizable formulation. Laser excitation of the nanoparticles embedded in the formulation reproducibly generates polymer features with typical dimensions ranging from 2 nm to a few tens of nanometer. We have determined the physicochemical parameters and mechanisms controlling the spatial extent of the photopolymerization process. We found that the diffusion of the dye is the main process limiting the polymerization reaction, as opposed to what is observed at the microscale with an equivalent chemical system. This approach demonstrates that plasmon-based polymerization can achieve true nanometer scale resolution and also provides a unique opportunity to investigate photochemistry at this length scale.