Citation: Liangliang Cai, Xinyi Zhang, Jiayi Lu, Juan Xiang, Qiang Sun, Andrew T.S. Wee. Disorder–order transition of two-dimensional molecular networks by selenium doping[J]. Chinese Chemical Letters, ;2026, 37(5): 111874. doi: 10.1016/j.cclet.2025.111874 shu

Disorder–order transition of two-dimensional molecular networks by selenium doping

Liangliang Cai ^{a, b, *,} ,
Xinyi Zhang ^a ,
Jiayi Lu ^a ,
Juan Xiang ^a ,
Qiang Sun ^a ,
Andrew T.S. Wee ^{b, *,}

a.
Materials Genome Institute, Shanghai University, Shanghai 200444, China
b.
Department of Physics, National University of Singapore, Singapore 117542, Singapore

cailiangliangmgi@shu.edu.cn

phyweets@nus.edu.sg

Received Date: 19 February 2025
Revised Date: 21 September 2025
Accepted Date: 22 September 2025
Available Online: 23 September 2025

Figures(5)

Geometrical configurations at the nanometer scale are inherently linked to electronic properties, offering exciting opportunity to engineer the latter through precise structural control. The honeycomb structure, a prominent geometry in two-dimensional materials like graphene, has become a versatile platform for advancing energy technologies, quantum computing, and nanoscale sensing. Achieving a perfect honeycomb network at large scale remains challenging but desired, especially when atomic defects and disorder can severely impact materials' properties and performances. Intrinsic topological defects often persist due to the conformational flexibility of the precursor skeletons, which allows precursor monomers to deform despite variations in preparation parameters. To address this challenge, we employ a tripod molecular precursor, pTBPT, combined with ultrahigh vacuum on-surface synthesis. Networks comprising rings of different edges are initially formed after deposition of pTBPT on Cu (111) at room temperature to 420 K. At low coverage (~0.015 monolayer) selenium doping, we achieve the fabrication of ordered honeycomb networks with much improved structural homogeneity. Selenium doping facilitated the formation of ordered two-dimensional metal-organic nanostructure from 360 K to 480 K. The disorder−order transition of molecular networks through selenium doping on Cu (111) is explored through high-resolution scanning tunneling microscopy (STM). A persistent homology method is resorted to quantify the degree of order of our patterns. The regulation of energy diagrams in the absence or presence of the selenium atom is revealed by density functional theory (DFT) calculations. These findings can enrich the on-surface synthesis toolbox of conformationally flexible precursors, for the design of ordered nanoarchitectures, and for future development of engineered honeycomb nanomaterials.
- On-surface synthesis,
- Conformationally flexible precursor,
- Selenium doping,
- Scanning tunneling microscopy (STM),
- Persistent homology (PH) method
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沈阳化工大学材料科学与工程学院沈阳 110142