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The short-wavelength sub-nanosecond luminescence in BaF 2 material, discovered in the early 80s, gave a new direction to research into fast scintillators and phosphors. In contrast to 'typical' luminescence occurring within the forbidden band gap, the new type of emission was due to transitions between the upper core and valence bands. Thus it was named core-valence luminescence (CVL); the terms cross-luminescence and Auger-free luminescence have also been used. Given its unusual nature, this new luminescence process has attracted considerable interest in the field of condensed matter physics. During the sequent decades (till the end of the previous century) CVL has been experimentally observed in several dozen compounds and the conditions for detecting CVL have been established. Interest in this kind of luminescence increased in recent years due to the emergence of new methods of crystal synthesis, the development of high-speed solid-state photodetectors, and the construction of unique modern set-ups using synchrotron radiation. This paper analyzes the numerous studies of CVL, obtained mainly over the past decade. Experimental and theoretical data on this topic are considered in detail. Special attention is given to new results on scintillation characteristics of BaF 2 in the form of single crystals, ceramics, nanoparticles, and composites. The features of CVL in binary and ternary compounds are discussed. Some Cs- and Ba-based ternary halides show relatively high light yields and represent promising fast scintillators. The prospects of using materials with CVL as fast scintillators for time-of-flight positron emission tomography and other applications are deliberated. • Overview of recent theoretical and experimental findings on Core Valence luminescence. • Most attractive CVL crystals for ultrafast scintillator applications analyzed. • Prospects for future studies and underexplored CVL materials listed. [ABSTRACT FROM AUTHOR]

Due to their reported fast decay times, Cs 2 ZnCl 4 and Cs 3 ZnCl 5 are promising candidates for detection of gamma rays and X-rays in high count rate and fast timing applications. In this work, we show that single crystals with better optical quality than previously demonstrated – and larger in size – can be grown via the vertical Bridgman method. Highly transparent Ø7 mm crystals of undoped Cs 2 ZnCl 4 and Cs 3 ZnCl 5 are grown and measured to have light yields surpassing those previously reported, achieving 1980 ± 100 ph/MeV and 1460 ± 70 ph/MeV at 662 keV – a 55% and 232% improvement, respectively. We observe single-component scintillation decay times for both Cs 2 ZnCl 4 (1.66 ns) and Cs 3 ZnCl 5 (0.82 ns) and radioluminescence emission with maximum intensity at ∼290 nm. Scalability of these materials is also evaluated based on growth of Ø22 mm crystals. Minimal cracking is observed, and the fast decay times are maintained at this size. Coincidence time resolution of 3 × 3 × 5 mm3 and 7 × 7 × 10 mm3 pixels cut from Ø22 mm Cs 2 ZnCl 4 are measured to be 148 ± 1 ps FWHM and 175 ± 1 ps FWHM, respectively. The improved performance and ability to be fabricated in large sizes now place Cs 2 ZnCl 4 and Cs 3 ZnCl 5 on the map as potential contenders for radiation detection applications where BaF 2 – the most commonly used ultrafast inorganic scintillator – is typically considered. • Single crystals of Cs 2 ZnCl 4 and Cs 3 ZnCl 5 were grown by the vertical Bridgman method. • Cs 2 ZnCl 4 had a scintillation decay time of 1.66 ns and light yield of 1980 ph/MeV at 662 keV. • Cs 3 ZnCl 5 had a scintillation decay time of 0.82 ns and light yield of 1460 ph/MeV at 662 keV. • The coincidence time resolution of Cs 2 ZnCl 4 was measured to be as good as 136 ± 2 ps FWHM. [ABSTRACT FROM AUTHOR]