Concentric dopant segregation in CVD-grown N-doped graphene single crystals

Heteroatom doping in graphene leads to bandgap opening and tunable electronic, magnetic and optical properties, which are important for graphene-based electronics applications. In recent years, scalable growth of nitrogen-doped graphene (NG) by chemical vapor deposition (CVD) has been extensively studied because of its potential for practical applications. A phenomenon that occurs exclusively for CVD-grown NG films is the segregation of doping concentration. However, most studies to date are conducted using highly polycrystalline NG films comprising small grain sizes. It is still unknown whether dopant segregation occurs in single crystalline NG domains. Here, we used hexamethylenetetramine ((CH2)6N4) as a single-source solid precursor to grow hexagonal-shaped monolayer NG single crystals of ∼20 µm on Cu substrates. The NG single crystals exhibit discrete concentric hexagonal rings comprising N depleted regions as determined by Raman spectroscopy. Supported by scanning tunneling microscopy experiments, we propose that the segregation of N dopants is caused by a competing N attachment mechanism to either zigzag or Klein edges during growth; where the former should result in higher N concentration and the latter with lower N concentration. This work provides critical insights into the growth mechanism of CVD-grown NG and enables new opportunities to engineer the properties of graphene by fabrication of lateral heterostructures.