Engineering Graphene Grain Boundaries for Plasmonic Multi-Excitation and Hotspots

Surface plasmons, merging photonics and electronics in nanoscale dimensions, have been the cornerstones in integrated informatics, precision detection, high-resolution imaging, and energy conversion. Arising from the exceptional Fermi–Dirac tunability, ultrafast carrier mobility, and high-field confinement, graphene offers excellent advantages for plasmon technologies and enables a variety of state-of-the-art optoelectronic applications ranging from tight-field-enhanced light sources, modulators, and photodetectors to biochemical sensors. However, it is challenging to co-excite multiple graphene plasmons on one single graphene sheet with high density, a key step toward plasmonic wavelength-division multiplexing and next-generation dynamical optoelectronics. Here, we report the heteroepitaxial growth of a polycrystalline graphene monolayer with patterned gradient grain boundary density, which is synthesized by creating diverse nanosized local growth environments on a centimeter-scale substrate with a polycrystalline graphene ring seed in chemical vapor deposition. Such geometry enables plasmonic co-excitation with varied wavelength diversification in the nanoscale. Via using high-resolution scanning near-field optical microscopy, we demonstrate rich plasmon standing waves, even bright plasmonic hotspots with a size up to 3 μm. Moreover, by changing the grain boundary density and annealing, we find the local plasmonic wavelengths are widely tunable, from 70 to 300 nm. Theoretical modeling supports that such plasmonic versatility is due to the grain boundary-induced plasmon–phonon interactions through random phase approximation. The seed-induced heteroepitaxial growth provides a promising way for the grain boundary engineering of two-dimensional materials, and the controllable grain boundary-based plasmon co-generation and manipulation in one single graphene monolayer will facilitate the applications of graphene for plasmonics and nanophotonics.