In situ synchrotron X-ray scission of polytetrafluoroethylene chains and elucidation of dry etching

We investigated the mechanism of polytetrafluoroethylene (PTFE) chain scission through in situ hard X-ray photoelectron spectroscopy at room temperature, 200 °C, and 230 °C. The C–C bonds in the main chain and C–F bonds in the side chains were broken, and F desorption from the PTFE surface was observed at room temperature. The formation of CF3 was also observed from the recombination of broken C–C bonds in the main chain and detached F, which were not induced by soft X-rays. In contrast, when the PTFE substrate was irradiated with hard X-rays at 200 °C, the CF3 intensity initially produced by recombination reactions decreased with irradiation time, and the photoelectron spectrum retained the original PTFE spectrum. Under these conditions, the F1s/C1s intensity ratio did not change with the irradiation time; hence, the fragment containing only CF2, the chemical composition of the original PTFE, was desorbed. When the substrate temperature was 230 °C, the CF3 intensity increased in relation to that at 200 °C. This result indicated that the formation of CF3 via recombination reactions of broken molecular chains is enhanced by thermal assistance. These phenomena were considered to be based on the balance between recombination and desorption by photochemical and pyrochemical reactions. These results will lead to a better understanding of the use of X-ray-irradiated fluorine resins and PTFE in potential space-based environments. This study will also promote the improvement of PTFE microfabrication methods and thin-film formation using synchrotron radiation. •PTFE chain hard X-ray scission observed in situ via hard XPS.•Hard X-rays induced main-chain C–C cleavage and CF3 via recombination reactions.•In situ observation of 200 °C PTFE etching, maintaining chemical composition.•PTFE etching via recombination–desorption balance upon photo/pyrochemical reactions.