AI 中文总结
本文基于第一性原理密度泛函理论，研究金属表面上石墨炔与二石墨炔分子线的自组装及电子性质，发现其可形成vdW金属-半导体异质结构，为低维分子电子器件提供了潜在平台。
AI 中文摘要
固体表面上的分子自组装是广泛研究的课题，其研究动机既来自基础科学兴趣，也来自技术应用需求。从基础研究角度看，这些研究旨在阐明控制分子自组装及所得表面结构的机制；从应用角度看，它们为控制表面反应和构建分子电子器件提供了途径。本文基于第一性原理密度泛函理论计算，对吸附在Au(111)、Ag(111)和Al(111)表面上的类石墨炔（GY(1D)）和类二石墨炔（GYD(1D)）结构组成的自组装分子线（MWs）开展了全面研究。总能计算表明，在三种金属基底上，非对齐的MW阵列在能量上更具优势。GY(1D)和GYD(1D)分子线通过范德华（vdW）力与金属表面相互作用，其分子轨道不参与金属界面态的形成。模拟X射线光电子能谱（XPS）显示，分子线的C 1s光谱特征在吸附后基本得以保留，而绝对结合能发生大幅下移，且该下移几乎与金属基底无关，表明金属屏蔽效应主导了吸附诱导的芯能级位移。电子能带结构计算进一步表明，分子线的半导体特性得以保留，形成了vdW金属-半导体异质结构，其中半导体组分由一维半导体通道构成。这些发现表明，金属表面上自组装的石墨炔基和二石墨炔基分子线为实现低维分子电子器件提供了有前景的平台。
英文摘要
Molecular self-assembly on solid surfaces has been the subject of extensive research, motivated by both fundamental and technological interests. On the fundamental side, these studies seek to elucidate the mechanisms governing molecular self-assembly and the resulting surface structures. From an applied perspective, they provide a route toward controlling surface reactions and engineering molecular electronic devices. Here, based on first-principles density functional theory calculations, we present a comprehensive study of self-assembled molecular wires (MWs), composed of graphyne (GY(1D)) and graphdiyne (GYD(1D))-like structures, adsorbed on Au(111), Ag(111), and Al(111) surfaces. Our total-energy calculations reveal that non-aligned MW arrays are energetically preferred on all three metal substrates. The GY(1D) and GYD(1D) molecular wires interact with the metal surfaces through van der Waals (vdW) forces, while their molecular orbitals do not contribute to the formation of metallic interface states. Simulated X-ray photoelectron spectroscopy (XPS) spectra reveal that the C 1s spectral features of the molecular wires are largely preserved upon adsorption, while the absolute binding energies undergo a substantial downshift that is nearly independent of the metal substrate, indicating that metallic screening effects dominate the adsorption-induced core-level shifts. Electronic band-structure calculations further show that the semiconducting character of the molecular wires is retained, resulting in vdW metal-semiconductor heterostructures in which the semiconducting component consists of one-dimensional semiconducting channels. These findings demonstrate that self-assembled graphyne- and graphdiyne-based molecular wires on metal surfaces provide a promising platform for the realization of low-dimensional molecular electronic devices.
