Depth profiling of microwave nitrogen-terminated polycrystalline diamond surfaces by energy-dependent X-ray photoelectron spectroscopy

Abstract

Nitrogen-terminated diamonds hold promise for stabilizing near-surface NV− centers, which is essential for reliable quantum sensing. Among various surface preparation methods, microwave (MW) nitrogen plasma, known for its minimal surface damage, appears as the most effective choice. In this investigation, we explore the nature of nitrogen bonding of polycrystalline diamond (PCD) surfaces exposed to MW nitrogen plasma using X-ray Photoelectron Spectroscopy (XPS) depth profiling and Near-Edge X-ray Absorption Fine Structure (NEXAFS) spectroscopy at the C K- and N K-edges. XPS depth profiling with atomic resolution, achieved by varying the probing photon energy using synchrotron radiation and supported by a physical model considering the associated inelastic mean free path, suggests a surface of almost fully saturated nitrogen in two main bonding configurations of similar contribution and a low coverage of ∼5 % of graphene-like islands residing atop the nitrogen-terminated diamond surface. The thermal stability of these surface groups is monitored by in situ annealing up to 700 °C. The depth profiles reveal that nitrogen atoms do not diffuse in the diamond crystal, resulting in excellent diamond crystallinity in the first atomic planes below the surface. C K-edge NEXAFS analysis reveals the position of unoccupied surface states within the diamond bandgap, opening new perspective on the stabilization of near-surface NV− centers.