This study investigates the complexation of iodine with polyvinylpyrrolidone (PVP) subjected to gamma irradiation at doses of 0, 10, 20, and 30 kGy. The complex formation involves I2 acting as a Lewis acid with electron-rich PVP as a Lewis base through a charge transfer mechanism. UV–visible spectroscopy revealed a red shift of the absorption peak at 337 nm for irradiated PVP-I2 samples, indicating stronger interactions between the triiodide ion (I3¯) and irradiated PVP. FTIR analysis confirmed the formation of new C≡N moieties arising from PVP-I2 complexation. The FT-Raman analysis revealed a new C≡N peak at 2360 cm−1 in irradiated PVP-I2 samples, with increasing intensity correlating to higher irradiation doses, indicating enhanced electron delocalization due to complex formation. XRD analysis showed that PVP-I2 samples irradiated at 0 and 10 kGy exhibited higher crystallinity than those irradiated at 20 and 30 kGy, suggesting that high-dose irradiation causes PVP radiolysis and ring opening. Dielectric measurements demonstrated enhanced polarizability and ionic conductivity of irradiated PVP-I2 films, related to structural disorder promoting charge dissociation and ion mobility. The direct bandgap decreased from 2.75 eV for unirradiated samples to 2.55 eV for samples irradiated at 30 kGy, indicating the creation of new optically active defect states. Urbach energy increased from 0.85 eV to 1.55 eV with increasing irradiation dose, confirming increased disorder in the PVP structure. These findings reveal that gamma irradiation significantly alters the optical and electrical properties of PVP-I2 films by creating defects and disrupting structure, offering new insights for tailoring these materials for optoelectronic applications.
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