Continuous photoluminescence, time resolved photoluminescence and optically detected magnetic resonance measurements of PbI2 nanometer-sized particles, embedded in SiO2 films

The nanometer sized particles of PbI₂ were embedded in SiO₂ films. X-ray diffraction and the TEM pictures showed the preservation of the bulk layered structure and symmetry. The PL spectrum of the nano-particles exhibited a pronounced blue shift of the exciton band due to quantum size effect. The Lead Iodide represents an exceptionally small exciton Bohr radius (a_B = 19 Å) and a special case in which m_e m_h. The prepared samples contained particles with mean radii, a, in the range a_B < a < 3a_B. Within this limit (with m_e m_h), the experimental results suggest that the electron is localized nearly at the center of the particle, enabling the hole to move around it. Thus, the size confinement permits the creation of an acceptor-like exciton. The PL spectrum revealed additional states, associated with stoichiometric defects either at the interior or surface sites of the nano-particles. These defects act either as donor or acceptor states. The dynamics of the various recombination processes has been investigated by measuring the time resolved PL spectra. The results show a multiexponential behavior of the various recombination emission bands, indicating the occurrence of trapping and detrapping processes. Analysis of these results suggests that the existence of surface states give rise to these complex radiative decay processes. The correlation between donor-acceptor recombination emission bands in the aforementioned samples and lattice imperfections was examined, utilizing optically detected magnetic resonance (ODMR) spectroscopy. The results identified the following imperfection sites: an acceptor site associated with an isotropic Lead vacancy defect, V⁻]_pb²⁺ and a donor site, associated with an anisotropic Iodine vacancy, V⁰]_Iodine.