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[en] Investigations on the chemical modifications induced by swift heavy ions in PMMA thin films were carried out using beams of high dE/dx (2.2 GeV Bi, 14,090 eV/nm) and low dE/dx (2 MeV H, 19 eV/nm). The induced chemical modifications were monitored by XPS for films with initial thickness of 50 and 100 nm. For both beams, the irradiation decreased the amount of carbon atoms bound to oxygen (C=O and C−O−C), with a larger decrease of the carboxyl moiety, as expected. However, the chemical changes induced by light and heavy ions were qualitatively different. For the same mean deposited energy density, proton irradiation induced a decrease of the relative intensity of the carbon–oxygen bonds up to ∼20% larger than the irradiation with Bi ions. This suggests a greater importance of particle ejection by unzipping of PMMA chains at high dE/dx, which tends to keep the O/C ratio closer to the pristine value.