Diffusion in photoresists is a fundamental process that significantly impacts micro-nano manufacturing. However, it often intertwines with chemical reactions, leading to intricate kinetics that compounds our comprehension. Here, we successfully applied all-atom molecular dynamics simulations to simultaneously describe the diffusion of acids and the deprotection reactions they catalyze in extreme ultraviolet photoresists, which are critical materials for high-resolution patterning. The results show that acids hop between binding sites with the aid of the other species present in photoresists, akin to observations of ion transport in organic electrolytes. The deprotection reactions enable acids to overcome spatially prohibitive barriers. These chemical reactions also create local free volume, facilitating the motion of the organic matrix and consequently promoting acid movement. We show that by simultaneously describing diffusion and chemical reactions, atomic-level simulations can reproduce the features of experimental reaction dynamics, highlighting the potential of molecular modeling in advancing photoresist design. These insights broaden our understanding of diffusion in organic solids and serve as a theoretical reference in the development of photoresists for higher performances.

中文翻译：

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化学扩增光刻胶中反应偶联酸扩散的微观机制


光刻胶中的扩散是显着影响微纳制造的基本过程。然而，它经常与化学反应交织在一起，导致错综复杂的动力学，使我们的理解更加复杂。在这里，我们成功地应用了全原子分子动力学模拟来同时描述酸的扩散及其在极紫外光刻胶中催化的脱保护反应，而极紫外光刻胶是高分辨率图案化的关键材料。结果表明，在光刻胶中存在的其他物质的帮助下，酸在结合位点之间跳跃，类似于对有机电解质中离子传输的观察。脱保护反应使酸能够克服空间上的阻碍障碍。这些化学反应还会产生局部自由体积，促进有机基质的运动，从而促进酸的运动。我们表明，通过同时描述扩散和化学反应，原子级模拟可以再现实验反应动力学的特征，突出了分子建模在推进光刻胶设计方面的潜力。这些见解拓宽了我们对有机固体中扩散的理解，并为开发更高性能的光刻胶提供了理论参考。