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KCaI 3 :Eu single crystals exhibit favorable scintillation properties and have potential for use in domestic security applications requiring radioisotope identification. The anisotropic thermal expansion of the orthorhombic unit cell of this perovskite-type scintillator has been investigated using in-situ high temperature X-ray diffraction on powdered samples. Samples from single crystals of both pure and Eu-doped KCaI 3 grown by the Bridgman method were used for comparison. Expansion with temperature along the b -axis is greatest with an average linear coefficient of thermal expansion of ≈ (41–46) x 10 −6  K −1 resulting from the weaker bonding between alternating layers of K and Ca parallel to the b -axis. Thermal expansion in each of the KCaI 3 samples has the highest degree of anisotropy with respect to the b and c axis with ratio ᾱ b /ᾱ c of 1.4–1.5. Additionally, we identify the predominant cleavage plane in KCaI 3 as (0 -3 -1) based upon Laue reflection imaging. [ABSTRACT FROM AUTHOR]

KCaI 3 :Eu crystals have been identified as very promising for use in spectroscopic detector applications related to nuclear nonproliferation and domestic security efforts. Initial studies have shown for small crystals a few mm 3 in size with 3% europium dopant concentration, a high light yield of >70,000 ph/MeV and energy resolution of ≈3% at 662 keV is attainable which is comparable with the highest performance scintillators discovered. In this work, single crystals of KCaI 3 with a range of Eu 2+ doping between 0 and 5 at% substituting for Ca 2+ were grown at 22 mm diameter and their performance for gamma-ray spectroscopy studied. Comparisons among crystals approximately Ø22 mm×22 mm (8.4 cm 3 or ≈0.5 in 3 ) provide a more accurate understanding of how scintillation performance changes with Eu doping and increased crystal size. KCaI 3 in the undoped form is shown to be a highly efficient intrinsic scintillator with a defect-related emission at 404 nm which coexists with the Eu 2+ 5d–4f emission in low dopant concentrations and is completely re-absorbed in more heavily doped crystals. For larger crystals, effects from self-absorption due to Eu activation become more evident by a near doubling of decay time for 0.5 in 3 crystals as the activator is increased from 0.5 to 5.0 at% Eu. Comparisons of pulse-height spectra obtained for Ø22 mm×22 mm cylinders with varying Eu concentration suggests best performance is achieved using lower Eu additions closer to 0.5–1.0 at%. Using a modified crystal packaging featuring an offset reflector geometry, 0.5 in 3 crystals of KCaI 3 :Eu can attain under 4% energy resolution at 662 keV. [ABSTRACT FROM AUTHOR]