Operando XPS for Plasma Process Monitoring: A Case Study on the Hydrogenation of Copper Oxide Confined under h-BN

We demonstrate that ambient pressure X-ray photoelectron spectroscopy (APXPS) can be used for in situ studies of dynamic changes in surface chemistry in a plasma environment. This opens a new and vast application space for XPS and greatly complements modern spectroscopy techniques to probe plasma–solid/liquid interactions relevant to process monitoring in the semiconductor industry, biomedical plasma applications, and plasma remediation technologies. Hexagonal boron nitride (h-BN) grown on Cu was used in this study as a well-defined model system for plasma process monitoring because of its unique chemical, optical, and electrical properties that make it a prospective material for advanced electronics. To better understand the stability and surface chemistry of h-BN during plasma-assisted processing, we track in real time the plasma-induced chemical state changes of B, N, and the underlying Cu substrate using APXPS equipped with an AC discharge plasma source operating at 13 Pa. Residual gas analysis mass-spectra were concurrently collected during plasma-XPS to track reaction products formed during plasma exposure. A clear reduction of CuxO is seen, while an h-BN layer remains intact, suggesting that hydrogen radical (H•) species can attack the exposed and h-BN-covered Cu oxide patches and partially reduce the underlying substrate without significantly damaging the overlaying h-BN, which is of practical importance for development of h-BN-encapsulated devices and interfaces. In addition to demonstration of plasma-XPS capabilities, we discuss the observed challenges (e.g., parasitic plasma-chamber wall reactions and charging effects) and propose potential solutions.