Films and crystalline powder of PbI2 intercalated with ammonia and pyridine

Thin films and crystalline powder of PbI2 intercalated with ammonia or pyridine have been studied by optical absorption, Raman scattering, photoluminescence, FTIR spectroscopy and thermo-gravimetric analysis. Ammonia intercalated PbI2 shows an increased optical band gap, of about 0.6 eV, with an intense broad emission band peaking at about 2.3 eV as signature in the photoluminescence spectrum. The intercalation of PbI2 with ammonia is noticed in the Raman spectrum by the appearance of new lines situated in low frequency range. The D-3d coordination geometry of Pb2+ in the PbI2 crystal is reduced by compression to orthorhombic one, the distribution of the electronic states in valence band is also changed. Thus, the top of the valence band undergo a deformation inducing a weakness of the interaction between the lead and iodine ions within a layer. Also the PbI2 intercalated with pyridine is featured by optical and vibration properties different that of pure crystalline powder. Finally, the intercalation of PbI2 with different molecules changes the basic semiconducting properties of the crystal. Thermal analyses and infrared absorption spectra have been used to study the desorption of guests species from PbI2 in order to evaluate the stability range and morphological changes with temperature.