Lyu Jing, Wong Zicong Marvin, Sun Haicheng, Yang Shuo-Wang, Xu Guo Qin
Department of Chemistry, National University of Singapore 3 Science Drive 3 117543 Singapore
Institute of High Performance Computing, Agency for Science, Technology and Research 1 Fusionopolis Way, #16-16 Connexis 138632 Singapore
Chem Sci. 2022 Apr 18;13(19):5674-5679. doi: 10.1039/d2sc00490a. eCollection 2022 May 18.
It is a long-standing goal to fabricate conductive molecular nanowires (NWs) on semiconductor surfaces. Anchoring molecules to pre-patterned surface nanostructures is a practical approach to construct molecular NWs on semiconductor surfaces. Previously, well-ordered inorganic Ge NWs were deduced to spontaneously grow onto Pt/Ge(001) surfaces after annealing at an elevated temperature. In this work, we further demonstrate that organic 7,7,8,8-tetracyanoquinodimethane (TCNQ) molecular NWs can self-assemble onto the atomic NWs on Pt/Ge(001) surfaces. The outer nitrogen atoms in TCNQ molecules hybridize with under-coordinated Ge atoms in Ge NWs with an energy release of ∼1.14 eV per molecule, and electrons transfer from Ge NWs to the frontier orbitals of anchored TCNQs resulting in a negatively charged state. This largely tailors the electronic configurations of TCNQs and Pt/Ge(001) surfaces, enhancing the electron transport along the dimer row direction. The TCNQ molecular NWs coupled with the Ge NWs represent an exemplary showcase for the fabrication of molecular NWs on semiconductor surfaces.
在半导体表面制造导电分子纳米线(NWs)是一个长期目标。将分子锚定到预先图案化的表面纳米结构上是在半导体表面构建分子纳米线的一种实用方法。此前,有序的无机锗纳米线被推断在高温退火后会自发生长在Pt/Ge(001)表面上。在这项工作中,我们进一步证明有机7,7,8,8 - 四氰基对苯二醌二甲烷(TCNQ)分子纳米线可以自组装到Pt/Ge(001)表面的原子纳米线上。TCNQ分子中的外部氮原子与锗纳米线中配位不足的锗原子杂化,每个分子释放约1.14 eV的能量,并且电子从锗纳米线转移到锚定的TCNQ的前沿轨道,导致带负电状态。这极大地调整了TCNQ和Pt/Ge(001)表面的电子构型,增强了沿二聚体行方向的电子传输。与锗纳米线耦合的TCNQ分子纳米线代表了在半导体表面制造分子纳米线的一个典型示例。