The Effect of Ionising Radiation on the Luminescence Properties of Fluoroperovskites

The luminescence of crystalline compounds can be used to monitor many physical phenomena, including doses of ionising radiation. Optically stimulated luminescence (OSL), thermoluminescence (TL), and radiophotoluminescence (RPL) have been successfully employed in dosimetry. However, few materials possess both the structural and luminescence properties required for medical dosimetry. This thesis aimed to investigate the luminescence features of the class of compounds known as fluoroperovskites. Emphasis was placed on studying the effects of irradiation on the luminescence properties, such that the compounds could be evaluated regarding potential applications in clinical dosimetry. Samples were primarily characterised using photoluminescence (PL), radioluminescence (RL), OSL, RPL, TL, and transmittance spectroscopy.  OSL was observed in the majority of samples due to the existence of electron trapping F-type centres. F-centre/Mn complexes were observed in all AMgF3:Mn compounds after irradiation and the energy levels of the complexes in each compound were experimentally determined. The most promising potential dosimeter host material was the near tissue-equivalent NaMgF3. When doped with Mn2+, the compound exhibited RPL via the formation of F-centre/Mn complexes and OSL via several trapping centres. The RPL could be probed independently to the OSL such that the compound could function as a hybrid OSL/RPL dosimeter. In the NaMgF3:Ln compounds, RPL occurred via the radiation-induced reduction Ln3+ → Ln2+ for Ln = Sm, Dy, and Yb. The reduction Sm3+ → Sm2+ was highly stable and could be non-destructively probed independently to the OSL. The Sm doped compound also exhibited radiation-induced conductivity that could be coupled with the RL, such that the compound could function as a real-time hybrid optical/electrical dosimeter. Charge kinetics, thermal quenching, and binding energy models were developed and applied to the compounds.   Finally, a two-dimensional readout system was designed and constructed. The capabilities of the system were evaluated using the OSL of NaMgF3:Eu and NaMgF3:Mn. Sensitivities to doses from < 10 mGy to > 1 Gy were obtained along with sub-millimetre spatial resolutions.