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蘸笔纳米刻印术(dip-pen nanolithography, DPN)作为一种独特的纳米加工手段, 具有在各类基底上书写精细图案的能力. 自20世纪末诞生以来, 研究者们对DPN中的墨水输运原理有了更深入的理解, 同时受惠于材料学的发展并结合复杂生化反应体系, 数种基于DPN衍生的纳米加工技术被开发出来. 与此同时, 依靠机械作用引发的一类化学反应, 即力化学(mechanochemistry), 在最近数十年来获得了越来越多的关注, 多种新颖的实验方法被引入. 本综述将介绍DPN及若干衍生技术的原理与应用, 以及力化学的机理与实现方法, 进而探讨结合这两者优势发展力化学打印的可能, 并揭示其在纳米技术及原子制造领域的应用前景.
As a unique nanomanipulation and nanofabrication tool, dip-pen nanolithography (DPN) has enjoyed great success in the past two decades. The DPN can be used to create molecular patterns with nanoscale precision on a variety of substrates with different chemistry properties. Since its advent, the DPN has been steadily improved in the sense of applicable inks, fabrication throughput, and new printing chemistry. Among these developments, mechanical force induced mechanochemistry is of special interest. In this review, we introduce the physical principles behind the DPN technique. We highlight the development of DPN for writing with various types of “inks”, including small molecules, viscous polymer solutions, lipids, and biomolecules, especially, the development of thermal-DPN allowing printing with inks that are usually in solid phase at room temperature. Next, we introduce the parallel-DPN and polymer pen nanolithography. These techniques greatly speed up the fabrication speed without sacrificing the precision. We also summarize the advances in chemical reaction based DPN technologies, including electrochemical DPN, metal tip-induced catalytical DPN, and mechanochemical DPN (or mechanochemical printing). To further elaborate the mechanism behind the mechanochemical printing, we briefly review the development of mechanochemistry, including the reaction mechanism, various experimental approaches to realizing mechanochemistry, and recent development in this field. We highlight the advantages of using atomic force microscopy to study mechanochemistry at a single molecule level and indicate the potential of combining this technique with DPN to realize mechanochemical printing. We envision that with the further discovery of novel mechanophores that are suitable for mechanochemical printing, this technique can be broadly applied to nanotechnology and atomic fabrication. -
Keywords:
- atomic force microscopy/
- single molecule force spectroscopy/
- mechanochemistry/
- dip-pen nanolithography
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调节变量 拉伸效果变化 增大超声强度 空化效应增强直至达到一个上限, 拉伸效果增强 增大溶剂蒸气压 空化效应受到气蚀缓冲而削弱, 拉伸效果降低 增大溶剂黏度 空化效应削弱, 拉伸效果降低 升高温度 导致溶剂蒸气压增大, 拉伸效果降低 提升聚合物浓度 导致溶剂黏度增大, 拉伸效果降低 
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纳米加工技术 加工尺度 技术优势 技术局限性 DPN 30—100 nm 快速书写; 高操控性 低通量, 低规模 t-DPN 100 nm—10 μm 可使用常温固态的墨料; 升温加速反应;
加工尺度一定程度上受温度调节墨料易扩散污染基底 Lipid-DPN 200—500 nm 磷脂预自组装可形成多层堆叠的立体结构 较难通过针尖控制纳米结构的形态 e-DPN 30—100 nm 可用于金属离子电镀、局部电改性 针尖电极的产物影响操控性 金属、生物催
化DPN80—150 nm 催化加工生物软材料的纳米结构 硬质陶瓷针尖易对软材料产生机械破坏 p-DPN 40—100 nm 多针尖, 大规模高通量纳米加工 成本昂贵 PPL 200 nm—50 μm 低成本大规模纳米加工 难以对针尖进行化学修饰;
弹性针尖受力大幅形变HSL 50 nm 尖端坚固不形变、精细度较高的大
规模聚合物笔纳米加工针尖制造流程复杂 DNL 25—75 nm 可控高精细度; 无扩散污染; 与三维刻蚀结合 针尖成本高、长时间受大机械力易损耗; 适用的
化学体系不多, 待进一步开发下载:
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