Chen Hou-Ju, Chu Yu-Hsun, Huang Po-Hsi, Kuo Chia-Nung, Lue Chin Shan, Lin Minn-Tsong
Department of Physics, National Taiwan University, Taipei 10617, Taiwan.
Department of Physics, National Cheng Kung University, Tainan 70101, Taiwan.
ACS Omega. 2025 Jul 22;10(35):39833-39840. doi: 10.1021/acsomega.5c03930. eCollection 2025 Sep 9.
By controlling the postannealing temperature, atomically flat supramolecular assemblies of perylene-3,4,9,10-tetracarboxylic dianhydride (PTCDA) with tunable structural and electronic properties were synthesized on an intercalated quasi-two-dimensional crystal, FeTaS, and characterized using scanning tunneling microscopy and spectroscopy (STM/STS). At 100 °C, a coexistence of a herringbone PTCDA assembly with p-type-like HOMO-LUMO alignment and a pseudosquare Fe-PTCDA structure were observed on the surface. Upon further annealing at 150 °C, a new dominant Fe-PTCDA honeycomb-kagome framework with chirality emerged, exhibiting n-type-like HOMO-LUMO characteristics. This transition in the types of HOMO-LUMO alignments, along with spatial variations in Fermi level shifting, is attributed to charge transfer from Fe atoms. These findings highlight the potential for designing functional materials, engineering interfacial properties, and constructing exotic low-dimensional structuressuch as kagome metal-organic frameworks (MOFs) and chiral nanostructuresthrough the controlled synthesis of organic heterostructures with emergent crystal phases.
通过控制退火后温度，在插层准二维晶体FeTaS上合成了具有可调结构和电子性质的苝-3,4,9,10-四羧酸二酐（PTCDA）原子级平整超分子组装体，并使用扫描隧道显微镜和光谱（STM/STS）对其进行了表征。在100°C时，在表面观察到具有p型类HOMO-LUMO排列的人字形PTCDA组装体和伪方形Fe-PTCDA结构共存。在150°C进一步退火后，出现了一种新的具有手性的主导Fe-PTCDA蜂窝- Kagome框架，表现出n型类HOMO-LUMO特征。HOMO-LUMO排列类型的这种转变，以及费米能级移动的空间变化，归因于Fe原子的电荷转移。这些发现突出了通过可控合成具有新兴晶相的有机异质结构来设计功能材料、调控界面性质以及构建奇异低维结构（如Kagome金属有机框架（MOF）和手性纳米结构）的潜力。
