Long-range ordered and atomic-scale control of graphene hybridization by photocycloaddition

Miao Yu*, Chong Chen, Qi Liu, Cristina Mattioli, Hongqian Sang, Guoqiang Shi, Wujun Huang, Kongchao Shen, Zhuo Li, Pengcheng Ding, Pengfei Guan, Shaoshan Wang, Ye Sun, Jinping Hu, André Gourdon, Lev Kantorovich, Flemming Besenbacher, Mingshu Chen, Fei Song, Federico Rosei

*Corresponding author for this work

Research output: Contribution to journalArticlepeer-review

37 Citations (Scopus)


Chemical reactions that convert sp2 to sp3 hybridization have been demonstrated to be a fascinating yet challenging route to functionalize graphene. So far it has not been possible to precisely control the reaction sites nor their lateral order at the atomic/molecular scale. The application prospects have been limited for reactions that require long soaking, heating, electric pulses or probe-tip press. Here we demonstrate a spatially selective photocycloaddition reaction of a two-dimensional molecular network with defect-free basal plane of single-layer graphene. Directly visualized at the submolecular level, the cycloaddition is triggered by ultraviolet irradiation in ultrahigh vacuum, requiring no aid of the graphene Moiré pattern. The reaction involves both [2+2] and [2+4] cycloadditions, with the reaction sites aligned into a two-dimensional extended and well-ordered array, inducing a bandgap for the reacted graphene layer. This work provides a solid base for designing and engineering graphene-based optoelectronic and microelectronic devices. [Figure not available: see fulltext.]

Original languageEnglish
Pages (from-to)1035-1041
Number of pages7
JournalNature Chemistry
Issue number11
Early online date18 Oct 2020
Publication statusPublished - 1 Nov 2020

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