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We report on the surface modification of polytetrafluoroethylene (PTFE) as anexample of soft- and bio-materials that occur under plasma discharge bykinetics analysis of radical formation using in situ real-time electron spinresonance (ESR) measurements. During irradiation with hydrogen plasma,simultaneous measurements of the gas-phase ESR signals of atomic hydrogen andthe carbon dangling bond (C-DB) on PTFE were performed. Dynamic changes of theC-DB density were observed in real time, where the rate of density change wasaccelerated during initial irradiation and then became constant over time. Itis noteworthy that C-DBs were formed synergistically by irradiation with bothvacuum ultraviolet (VUV) and atomic hydrogen. The in situ real-time ESRtechnique is useful to elucidate synergistic roles during plasma surfacemodification.

Synergistic Formation of Radicals by Irradiation with Both Vacuum Ultraviolet and Atomic Hydrogen: A Real-Time In Situ Electron Spin Resonance Study