Electron-beam induced methane decomposition for in-situ carbon doping of hexagonal boron nitride
Controlling the spatial incorporation of carbon into hexagonal boron nitride (hBN) is essential for engineering optically active defects, yet existing approaches lack nanoscale precision and control over the carbon supply. Here, we demonstrate a method for carbon doping of hBN using electron-beam irradiation in a low-pressure methane atmosphere, where the beam simultaneously generates vacancies and decomposes methane into individual carbon and hydrogen atoms. Using annular dark-field scanning transmission electron microscopy, we show that increasing the methane partial pressure suppresses pore growth and drives the formation of triangular boron-terminated pores through preferential hydrogen etching of nitrogen. Time-resolved electron energy-loss spectroscopy (EELS) mapping reveals progressive carbon incorporation into the lattice, accompanied by boron and nitrogen depletion. Carbon clustering occurs predominantly within the irradiated area: 84+-7% of carbon-rich regions are confined to the area exposed to the electron beam, while some carbon atoms are also found to diffuse up to an average distance of 4.7+-0.5 nm beyond it. The incorporated carbon atoms arrange in a hexagonal pattern within the lattice, forming patches that do not exceed ~1 nm in size. Analysis of the EELS fine structure indicates modifications to the local electronic environment within these regions, with implications for the optical properties of the resulting carbon-related defects.