四氰基苯基卟啉在半导体CoO（100）膜上的吸附、自组装和自金属化
Adsorption, self-assembly and self-metalation of tetra-cyanophenyl porphyrins on semiconducting CoO(100) films
摘要：
采用低温扫描隧道显微镜和光谱（STM/STS）结合密度泛函理论（DFT）研究了超高真空下游离碱5，10，15，20-四（对氰基苯基）卟啉（2 H-TCNPP）在Au（111）表面岩盐（rs）CoO（100）薄膜上的吸附性质.在Au（111）上制备了在合适厚度范围内具有优异质量的rs-CoO（100）膜。特别是，我们发现，只有1纳米厚的薄膜显示半导体的能隙$E_\mathrm{g}=(2.5\pm 0.2)\,\textrm{eV}$。2 H-TCNPP在300 K下沉积后，在80 K下稳定地在水溶液中进行长程有序的超结构自组装。用密度泛函理论分析了分子在自组装体表面和内部的吸附几何。我们发现，自组装稳定的氢桥键通过功能氰基。我们的STS数据显示的CoO的基本间隙内的分子状态。通过与计算的DOS的比较，我们确定的前线轨道的能量位置，并发现，前三个LUMO态2 H-TCNPP位于带隙内，而HOMO是移动1 eV以下的CoO导带边。退火到420 K时，分子在STM图像中改变了它们的外观，并形成了位于分子中心的新的突出电子态。我们解释这种变化的配置作为Co-TCNPP创建的氧化物表面上的自金属化。
英文摘要：
The adsorption properties of free base 5,10,15,20-tetrakis(p-cyanophenyl)porphyrin (2H-TCNPP) on thin films of rock salt (rs) CoO(100) on Au(111) was studied in ultra-high vacuum by a combination of low-temperature scanning tunneling microscopy and spectroscopy (STM/STS) and density functional theory (DFT). Films of rs-CoO(100) on Au(111) are prepared with excellent quality in a suitable thickness range. Particularly, we found that films of only 1 nm thickness show a semiconducting energy gap of $E_\mathrm{g}=(2.5\pm 0.2)\,\textrm{eV}$. Upon deposition at 300 K, 2H-TCNPP adsorbs flat-lying and self-assembles in a long-range ordered superstructure that is stable at 80 K. The adsorption geometry of the molecules on the surface and within the self-assembly is analyzed by DFT. We find that the self-assemblies are stabilized by hydrogen bridge bonding via the functional cyano groups. Our STS data shows molecular states within the fundamental gap of the CoO. By comparison with the calculated DOS we determine the energetic positions of the frontier orbitals and find that the first three LUMO states 2H-TCNPP are located within the band gap, whereas the HOMO is shifted 1 eV below the CoO conduction band edge. Upon annealing to 420 K the molecules change their appearance in STM images and a new prominent electronic state located at the center of the molecule is formed. We interpret this changed configuration as Co-TCNPP created by self-metalation on the oxide surface.
机构、总结、中文摘要均由AI分析而来，可能存在错误，请以论文正文为准。
