Chen Weizhou, Wang Liming, Wang Zi-Rui, Zhu Tao, Ye Yuting, Li Qiao-Hong, Yi Xiaofeng, Zhang Jian
State Key Laboratory of Structural Chemistry, Fujian Institute of Research on the Structure of Matter, Chinese Academy of Sciences, Fuzhou, Fujian, 350002, P. R. China.
College of Chemistry, Fuzhou University, Fuzhou, Fujian, 350108, P. R. China.
Angew Chem Int Ed Engl. 2025 Jan 10;64(2):e202414360. doi: 10.1002/anie.202414360. Epub 2024 Nov 9.
Tin-oxo clusters are increasingly recognized as promising materials for nanolithography technology due to their unique properties, yet their structural impacts on lithography performance remain underexplored. This work explores the structural impacts of heterometal strategies on the performance of tin-oxo clusters in nanolithography, focusing on various metal dopants and their coordination geometries. Specifically, SnOC-1(In), SnOC-1(Al), SnOC-1(Fe), and SnOC-2 were synthesized and characterized. These clusters demonstrate excellent solubility, dispersibility, and stability, facilitating the preparation of high-quality films via spin-coating for lithographic applications. Notably, this work innovatively employs Atomic Force Microscopy-based Infrared Spectroscopy (AFM-IR), neutron reflectivity (NR), and X-ray reflectivity (XRR) measurements to confirm film homogeneity. Upon electron beam lithography (EBL), all four materials achieve 50 nm line patterns, with SnOC-1(In) demonstrating the highest lithography sensitivity. This enhanced sensitivity is attributed to indium dopants, which possess superior EUV absorption capabilities and unsaturated coordination environments. Further studies on exposure mechanisms indicated that Sn-C bond cleavage generates butyl free radicals, promoting network formations that induce solubility-switching behaviors for lithography. These findings underscore the efficacy of tailored structural design and modulation of cluster materials through heterometal strategies in enhancing lithography performance, offering valuable insights for future material design and applications.
锡氧簇由于其独特的性质，越来越被认为是纳米光刻技术中很有前景的材料，然而它们对光刻性能的结构影响仍未得到充分探索。这项工作探讨了异金属策略对纳米光刻中锡氧簇性能的结构影响，重点关注各种金属掺杂剂及其配位几何结构。具体而言，合成并表征了SnOC-1(In)、SnOC-1(Al)、SnOC-1(Fe)和SnOC-2。这些簇表现出优异的溶解性、分散性和稳定性，便于通过旋涂制备用于光刻应用的高质量薄膜。值得注意的是，这项工作创新性地采用基于原子力显微镜的红外光谱（AFM-IR）、中子反射率（NR）和X射线反射率（XRR）测量来确认薄膜的均匀性。在电子束光刻（EBL）中，所有四种材料都实现了50 nm的线条图案，其中SnOC-1(In)表现出最高的光刻灵敏度。这种增强的灵敏度归因于铟掺杂剂，其具有优异的极紫外吸收能力和不饱和配位环境。对曝光机制的进一步研究表明，Sn-C键的断裂产生丁基自由基，促进网络形成，从而诱导用于光刻的溶解度转换行为。这些发现强调了通过异金属策略进行定制结构设计和调节簇材料在提高光刻性能方面的有效性，为未来的材料设计和应用提供了有价值的见解。
