Scalable Synthesis and Characterization of Multilayer γ-Graphyne, New Carbon Crystals with a Small Direct Band Gap

$\gamma$-Graphyne is the most symmetric sp2/sp1 allotrope of carbon, which can be viewed as graphene uniformly expanded through insertion of two-carbon acetylenic units between all the aromatic rings. To date, synthesis of bulk $\gamma$-graphyne has remained a challenge. We here report the synthesis of multilayer $\gamma$-graphyne through crystallization-assisted irreversible cross-coupling polymerization. Comprehensive characterization of this new carbon phase is described, including synchrotron X-ray diffraction, electron diffraction, lateral force microscopy, Raman and infrared spectroscopy, and cyclic voltammetry. Experiments indicate that $\gamma$-graphyne is a 0.48 eV bandgap semiconductor, with a hexagonal a-axis spacing of 6.88 Å and an interlayer spacing of 3.48 Å, which is consistent with theoretical predictions. The observed crystal structure has an aperiodic sheet stacking. The material is thermally stable up to 240 $^\circ$C but undergoes a transformation at higher temperatures. While conventional 2D polymerizations and reticular chemistry rely on error correction through reversibility, we demonstrate that a periodic covalent lattice can be synthesized under purely kinetic control. The reported methodology is scalable and inspires extension to other allotropes of the graphyne family.