Covalent 2D Patterning, Local Electronic Structure and Polarization Switching of Graphene at the Nanometer Level

Abstract

A very facile and efficient protocol for the covalent patterning and properties tuning of graphene is reported. Highly reactive fluorine radicals were added to confined regions of graphene directed by laser writing on graphene coated with 1‐fluoro‐3,3‐dimethylbenziodoxole. This process allows for the realization of exquisite patterns on graphene with resolutions down to 200 nm. The degree of functionalization, ranging from the unfunctionalized graphene to extremely high functionalized graphene, can be precisely tuned by controlling the laser irradiation time. Subsequent substitution of the initially patterned fluorine atoms afforded an unprecedented graphene nanostructure bearing thiophene groups. This substitution led to a complete switch of both the electronic structure and the polarization within the patterned graphene regions. This approach paves the way towards the precise modulation of the structure and properties of nanostructured graphene.

Microemulsions for the covalent patterning of graphene

“…This approach relies on laser-triggered photolysis for the selective and reversible patterning of graphene, involving silver nanoparticles to generate trifluoromethyl radicals, which requires an external source for a laser-induced patterning. [17][18][19][20] While these approaches represent the ultimate degree of control with regards to resolution, down to atomic scale, they all require complicated nanofabrication techniques and equipment. Recently, self-assembled molecular networks have been used to achieve patterning with few nm periodicity, partly overcoming this problem, but relying instead on a very specific molecular design.…”

Exploring the effect of the covalent functionalization in graphene-antimonene heterostructures

“…Actually, the covalent bond formation in graphene mediated by radicals has been widely reported in the literature. 58–61 For this, we applied a recent laser-induced functionalization protocol developed by Hirsch and co-workers 62–69 using dibenzoyl peroxide (DBPO) to graft phenyl groups on the surface of graphene according to Fig. 3a.…”

Recent Progress and Perspective of an Evolving Carbon Family From 0D to 3D: Synthesis, Biomedical Applications, and Potential Challenges

“…These intriguing 2D nanomaterials have gained considerable attention, in addition to the constant intrinsic luminescence as well in FL biosensors focused on Förster resonance energy transfer (FRET), as nanoquenchers with high FL, high biocompatibility, and potential electronics applications. , Two separate mechanisms are now widely agreed to account for the production of PL in graphene nanomaterial caused by the conjugated π domain and by the defect-derived PL emissions. This mechanism transfers photoexcitation energy from the fluorophore donor to the molecule of the receptor, depending on the spectral overlap between the donor emissions and the receiver absorption.…”