Optical and structural transformations in polyethylene terephthalate (PET) films subjected to Ag+-ion implantation and subsequent Au7+-ion irradiation

Abstract

We report on the dual effects of ion implantation and swift heavy ion on the optical and structural characteristics of polyethylene terephthalate (PET) films using UV–Vis spectrophotometry, FTIR and X-ray diffraction measurements. Samples were first implanted with 150 keV Ag${}^{+}$-ions at different fluences of 1 $\times 10^{16}$, 5 $\times 10^{16}$, and 1 $\times 10^{17}$ ions/cm${}^2$, and thereafter irradiated with 30 MeV Au${}^{7+}$-ions at different fluences, while analysing elemental depth profile in situ on the Time of Flight Heavy Ions Elastic Recoil Detection (ToF-Hi-ERDA) instrument. The elemental depth profile measurements showed considerable atomic depletion of hydrogen from 36% down to below 6% and oxygen from 18% to about 5%. The proportion of carbon increased from 45% to over 87%. The optical bandgap decreased with increasing ion implantation fluence and reduced even further on irradiation with 30 MeV ¹⁹⁷Au${}^{7+}$-ions. The most notable outcome of the implantation was the onset of the precipitation of gold nanoparticles (Au-NPs) in the PET matrix, marked by Localised Surface Plasmon Resonance effects, coincided with a relatively significant drop in the bandgap energy. This latter effect could only be best explained as the result of these Au-NPs in the PET. This suggests that optical bandgap tuning in polymer films, usually achievable through high fluence implantation at low energy (i.e., keV), could also be realized through low fluence irradiation with MeV energy ions. It is surmised that, for the noble metals, NP-induced bandgap modification in PET precludes the need for high fluence to achieve the same. This has the obvious advantage of bandgap alterations at much lower structural damage to the target polymer. As reported by FTIR results, one can observe structural changes with the formation of new chemical bonds on thin films. X-ray diffraction results exhibited one prominent peak corresponding to the (100) plane, which varies in intensity with increased implantation fluence, suggesting a change in the crystallinity of the PET. The decrease in (100) peak or crystallinity was well connected with the presence and decrease of 847, 970, and 1471 cm⁻¹ peaks, which were assigned to the ethylene glycol molecular groups.