On-Surface Synthesis of Variable Bandgap Nanoporous Graphene

Tuning the bandgap of nanoporous graphene is desirable for applications such as the charge transport layer in organic-hybrid devices. The holy grail in the field is the ability to synthesize 2D nanoporous graphene with variable pore sizes, and hence tunable band gaps. Herein, the on-surface synthesis of nanoporous graphene with variable bandgaps is demonstrated. Two types of nanoporous graphene are synthesized via hierarchical CC coupling, and are verified by low-temperature scanning tunneling microscopy and non-contact atomic force microscopy. Nanoporous graphene-1 is non-planar, and nanoporous graphene-2 is a single-atom thick planar sheet. Scanning tunneling spectroscopy measurements reveal that nanoporous graphene-2 has a bandgap of 3.8 eV, while nanoporous graphene-1 has a larger bandgap of 5.0 eV. Corroborated by first-principles calculations, it is proposed that the large bandgap opening is governed by the confinement of π-electrons induced by pore generation and the non-planar structure. The finding shows that by introducing nanopores or a twisted structure, semi metallic graphene is converted into semiconducting nanoporous graphene-2 or insulating wide-bandgap nanoporous graphene-1.