标题： 分子工具用于非平面表面化学 显示英文标题

标题： Molecular Tools for Non-Planar Surface Chemistry

摘要： 扫描探针显微镜（SPM）对钝化硅表面的表面化学研究仅显示了平面内的化学反应，而对裸露硅的研究在分子附着后促进额外反应方面有限。 在这里，我们通过选择性吸附三维、硅特异性的“分子工具”实现了Si(100)上的后续反应。 在激活步骤之后，这些分子呈现出一个垂直于平面的自由基，既可以捐赠也可以接受分子片段，从而实现了多种尺度的应用，例如宏观尺度的可定制硅碳涂层或纳米尺度的探针介导的机械合成。 通过广泛分子设计标准可以创建许多这样的分子工具，这些标准促进了可重复性、表面特异性和实验可验证性。 这些标准通过一种模型分子工具四碘甲基锗烷（$Ge(CH_{2}I)_{4}$；TIMe-Ge）进行了演示，实验验证通过SPM和X射线光电子能谱（XPS）进行，理论支持则通过密度泛函理论（DFT）研究提供。 有了这个框架，在硅上启用了广泛且多样的新分子工程技术能力。 显示英文摘要

摘要： Scanning probe microscopy (SPM) investigations of on-surface chemistry on passivated silicon have only shown in-plane chemical reactions, and studies on bare silicon are limited in facilitating additional reactions post-molecular-attachment. Here, we enable subsequent reactions on Si(100) through selectively adsorbing 3D, silicon-specific "molecular tools". Following an activation step, the molecules present an out-of-plane radical that can function both to donate or accept molecular fragments, thereby enabling applications across multiple scales, e.g., macroscale customizable silicon-carbon coatings or nanoscale tip-mediated mechanosynthesis. Creation of many such molecular tools is enabled by broad molecular design criteria that facilitate reproducibility, surface specificity, and experimental verifiability. These criteria are demonstrated using a model molecular tool tetrakis(iodomethyl)germane ($Ge(CH_{2}I)_{4}$; TIMe-Ge), with experimental validation by SPM and X-ray photoelectron spectroscopy (XPS), and theoretical support by density functional theory (DFT) investigations. With this framework, a broad and diverse range of new molecular engineering capabilities are enabled on silicon.