Li Jun, Piquero-Zulaica Ignacio, Gottardi Stefano, Ashoush Mustafa A, Abd El-Fattah Zakaria M, Solianyk Leonid, Ortega Jose Enrique, Barth Johannes V, Moreno-Lopez Juan Carlos, Lobo-Checa Jorge, Stöhr Meike
Zernike Institute for Advanced Materials, University of Groningen, 9747 AG Groningen, Nijenborgh 3, Netherlands.
Centro de Física de Materiales CSIC/UPV-EHU, Manuel Lardizabal 5, 20018 San Sebastian, Spain.
Nanoscale. 2025 Apr 17;17(16):10314-10323. doi: 10.1039/d5nr00148j.
The periodic herringbone reconstruction on the surface of Au(111) consists of alternating face-centered-cubic (fcc) and hexagonal-closed-packed (hcp) sites separated by dislocation lines and elbows. This well-known arrangement acts as an electronic superlattice for surface-state electrons, creating a mini-gapped band structure with a modulated electronic density. This rich and fascinating geometrical and electronic landscape has countless times served as a platform for molecular self-assembly and on-surface synthesis of carbon-based nanoarchitectures as well as a template for 2D material growth. In this work, we fabricated a long-range ordered organic quantum corral (QC) array the self-assembly of 1,3,5-benzenetribenzoic acid molecules onto the herringbone reconstructed Au(111) surface. The periodicity of this QC array is nearly half the one of the underlying Au herringbone reconstruction, enabling us to study the delicate interplay between the two potential landscapes by allowing the selective formation and electronic modulation of QCs both on hcp and fcc sites. Scanning tunneling microscopy/spectroscopy (STM/STS) can probe such local differences in the first partially confined state and finds that not only the energy onset of the surface state electrons is influenced but also the modulation of the shallow herringbone potential contributes to the newly formed band structure. This is confirmed by angle-resolved photoemission spectroscopy (ARPES), where the interplay of the periodic potentials introduced by the organic QC array and herringbone reconstruction results in the formation of a distinct surface state band structure. These results are corroborated and intuitively understood with electron-plane-wave expansion (EPWE) simulations. Our work shows that combined molecular and non-organic patterning can serve as a promising tool to macroscopically tune the electronic properties of metal surfaces in a controllable manner.
金（111）表面的周期性人字形重构由面心立方（fcc）和六方密排（hcp）位点交替组成，这些位点由位错线和肘状结构分隔。这种广为人知的排列方式作为表面态电子的电子超晶格，形成了具有调制电子密度的微带隙能带结构。这种丰富而迷人的几何和电子景观无数次地成为分子自组装和碳基纳米结构的表面合成的平台，以及二维材料生长的模板。在这项工作中，我们通过将1,3,5-苯三苯甲酸分子自组装到金（111）表面的人字形重构结构上，制备了一种长程有序的有机量子围栏（QC）阵列。该QC阵列的周期性几乎是底层金的人字形重构结构的一半，这使我们能够通过在hcp和fcc位点上选择性地形成QC并对其进行电子调制，来研究这两种潜在景观之间的微妙相互作用。扫描隧道显微镜/光谱（STM/STS）可以探测到在第一个部分受限状态下的这种局部差异，并发现不仅表面态电子的能量起始点受到影响，而且浅人字形势的调制也对新形成的能带结构有贡献。角分辨光电子能谱（ARPES）证实了这一点，其中有机QC阵列和人字形重构引入的周期性势的相互作用导致形成了独特的表面态能带结构。这些结果通过电子平面波展开（EPWE）模拟得到了证实和直观理解。我们的工作表明，分子和非有机图案化相结合可以作为一种有前途的工具，以可控的方式宏观地调节金属表面的电子性质。
