Tuning the structure of CsCaI₃:Eu via substitution of bromine for iodine

CsCaI₃:Eu is a promising scintillator material that can be grown from the melt, but undergoes a tetragonal to orthorhombic phase transition upon cooling at 255 °C, causing twinning and cloudiness. The purpose of this work is to suppress this solid to solid phase transition in the CsCaI₃:Eu scintillator, which has a light yield of ∼40000 ph/MeV and energy resolution at 662 keV of ∼4%, by halide replacement to form the compound CsCaBr_xI_3-x. Crystals 8 cm³ in volume were grown using the vertical Bridgman method with varying bromine content from x = 0.2 to x = 1, resulting in improved transparency for crystals with bromine content x > 0.6. Powder X-ray diffraction data coupled with differential scanning calorimetry and radioluminescence measurements were used to investigate structural modifications, melting point dependence and spectral emission dependence on the bromine/iodine ratio. Partial replacement of iodine by bromine improves optical quality and scintillation properties by stabilizing the structure, rendering it useful for isotope identification for national security applications. The composition CsCaBr_0.8I_2.2:Eu was determined to be the best combination of improved structure and performance, and larger 22 and 38 mm Ø crystals were grown for further evaluation. Large size slabs of these crystals showed good crystal quality and improved performance over CsCaI₃Eu with 8.4% and 9.5% energy resolution at 662 keV, respectively.