ABSTRACT
We present here a novel experimental study of changes after contact electrification in the optical transmission spectra of samples of both pristine and irradiated PET film treated with Kr+15 ions of energy of 1.75 MeV and a fluence of 3 × 1010 cm2. We used a non-standard electrification scheme for injecting electrons into the film by applying negative electrodes to both its surfaces and using the positively charged inner regions of the film itself as the positive electrode. Electrification led to a decrease in the intensity of the internal electric fields for both samples and a hypsochromic (blue) shift in their spectra. For the irradiated PET sample, electrification resulted in a Gaussian modulation of its optical properties in the photon energy range 2.3-3.6 eV. We associate this Gaussian modulation with the partial decay of non-covalent extended conjugated systems that were formed under the influence of the residual radial electric field of the SHI latent tracks. Our studies lead us to suggest the latent track in the PET film can be considered as a variband material in the radial direction. Consideration of our results along with other published experimental results leads us to conclude that these can all be consistently understood by taking into account both the swift and slow electrons produced by SHI irradiation, and that it appears that the core of a latent track is negatively charged, and the periphery is positively charged.
ABSTRACT
The novelty of the study is that the ordering that occurs in a PET film under the action of SHI irradiation manifests itself as an increase in the integral intensity of intrinsic luminescence. The Urbach behaviour of the red shift of the absorption edge is used as a baseline for further analysis of experimental optical transmission spectra of PET films irradiated by swift heavy ions (SHI) previously published by the authors. Negative deviations of the experimental spectra from the Urbach baseline in the visible and UV parts of the spectrum are attributed to enhanced by SHI irradiation intrinsic luminescence. The observed dependence of the integral intensity of luminescence of irradiated PET films on the SHI fluence and ion charge provides further confirmation of the presence of SHI-induced ordering of the molecular structure in SHI latent tracks.
ABSTRACT
This paper presents a new analysis of the experimental transmission spectra of polyethylene terephthalate (PET) films before and after irradiation with swift heavy ions (SHI) films, as reported previously by the authors. It is shown that the absorption edge red shift for irradiated films contains two regions of exponential form, one of which is located in the UV region and the other at lower energy, mainly in the visible part of the spectrum. The behaviour of the transmission curves under different irradiating fluences demonstrates that these two regions reflect respectively the electron-enriched core of the latent track and its electron-depleted peripheral halo. The focal point method yields a bandgap energy of 4.1 eV for the electron-enriched core of the latent track, which is similar to n-doped semiconductors, and a bandgap of about 1.3-1.5 eV for the electron-depleted halo, similar to p-doped semiconductors. The boundary between the latent track cores and halos corresponds to a conventional semiconductor p-n junction. The values of the characteristic Urbach energy determined from experimental data correspond to the nonradiative transition energy between the excited singlet and triplet levels of benzene-carboxyl complexes in repeat units of the PET chain molecule. A parallel is drawn between the SHI-induced redistribution of electrons held in structural traps in the PET film and chemical redox reactions, which involve the redistribution of electrons in chemical bonds. It is suggested that alkali etching triggers the release of excess electrons in the latent track cores, which act as a catalyst for the fragmentation of PET chain molecules along the latent tracks of the SHI irradiation.
ABSTRACT
This paper presents the results of a study of polyethylene terephthalate (PET) films irradiated with Ar and Kr ions at both normal orientation and an angle of 40° to the normal. Normal irradiation was performed using Ar8+ and Kr15+ ions with an energy of 1.75 MeV/au and fluences in the range (2-500) × 1010 cm-2 for Ar8+ ions and (1.6 - 6.5) × 1010 cm-2 for Kr15+ ions. Kr ions with an energy of 1.2 MeV/au and charges of 13+, 14+, and 15+ were used for angled irradiation. For each Kr ion charge value, three fluence values were used: 5 × 1010, 1 × 1011, and 2.5 × 1011 cm-2. It is well known that irradiation of PET films by swift heavy ions results in a red shift of the UV-vis transmission spectra absorption edge. The experimental transmission spectra exhibit well-defined interference fringes, which obscure the underlying transmission response. Using an existing technique to obtain interference-free transmission curves Tα(λ) for both pristine and irradiated PET film samples, we found that S, the total radiation-induced absorption of light by the PET film, is proportional to the logarithm of the fluence F. In addition to this dependence on the irradiating fluence, we also found that the charge of the irradiating ion has a significant influence on the position of the absorption edge in the UV-vis spectra. This provides experimentally independent evidence to confirm our previous results showing that ion charge has an effect on the post-irradiation state of PET films. We present a physical interpretation of the observed absorption edge red shift in irradiated PET films as being due to the growth of extended conjugated systems via the formation of intermolecular helical structures. Our investigations into the stability of irradiation-induced effects in PET films show that comparison of UV-vis transmission spectra before and after annealing can provide information about the structure of deep traps in PET.
