Single-atom spectroscopy of phosphorus dopants implanted into graphene

One of the keys behind the success of modern semiconductor technology has been the ion implantation of silicon, which allows its electronic properties to be tailored. For similar purposes, heteroatoms have been introduced into carbon nanomaterials both during growth and using post-growth methods. However, due to the nature of the samples, it has been challenging to determine whether the heteroatoms have been incorporated into the lattice as intended. Direct observations have so far been limited to N and B dopants, and incidental Si impurities. Furthermore, ion implantation of these materials is challenging due to the requirement of very low ion energies and atomically clean surfaces. Here, we provide the first atomic-resolution imaging and electron energy loss spectroscopy (EELS) evidence of phosphorus atoms in the graphene lattice, implanted by low-energy ion irradiation. The measured P L _2,3-edge shows excellent agreement with an ab initio spectrum simulation, conclusively identifying the P in a buckled substitutional configuration. While advancing the use of EELS for single-atom spectroscopy, our results demonstrate the viability of phosphorus as a lattice dopant in sp ²-bonded carbon structures and provide its unmistakable fingerprint for further studies. (letter)