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Historically, the discovery and optimization of doped bulk materials has been predominantly developed through an Edisonian approach. While successful and despite the constant progress in fundamental understanding of detector materials physics, the pr ocess has been restricted by its inherent slow pace and low success rate. This poor throughput owes largely to the considerable compositional space that needs to be accounted for to fully comprehend complex material/performance relationship. Here, we present a combinatorial approach where doped bulk scintillator materials can be rapidly optimized for their properties through concurrent extrinsic doping/co-doping strategies. The concept that makes use of Design of Experiment, rapid growth and evaluation techniques, and multivariable regression analysis, has been successfully applied to the engineering of NaI performance, a historical but mediocre performer in scintillation detection. Using this approach, we identified a three-element doping/co-doping strategy that significantly improves the material performance. The composition was uncovered by simultaneously screening for a beneficial co-dopant ion among the alkaline earth metal family and by optimizing its concentration and that of Tl+ and Eu2+ ions. The composition with the best performance was identified as 0.1% mol Tl+, 0.1% mol Eu2+ and 0.2% mol Ca2+. This formulation shows enhancement of energy resolution and light output at 662 keV, from 6.3 to 4.9%, and from 44,000 to 52,000 ph/MeV, respectively. The method, in addition to improving NaI performance, provides a versatile framework for rapidly unveiling complex and concealed correlations between material composition and performance, and should be broadly applicable to optimization of other material properties.
We generalize and systematize basic experimental data on optical and luminescence properties of ZnO single crystals, thin films, powders, ceramics, and nanocrystals. We consider and study mechanisms by which two main emission bands occur, a short-wav elength band near the fundamental absorption edge and a broad long-wavelength band, the maximum of which usually lies in the green spectral range. We determine a relationship between the two luminescence bands and study in detail the possibility of controlling the characteristics of ZnO by varying the maximum position of the short-wavelength band. We show that the optical and luminescence characteristics of ZnO largely depend on the choice of the corresponding impurity and the parameters of the synthesis and subsequent treatment of the sample. Prospects for using zinc oxide as a scintillator material are discussed. Additionally, we consider experimental results that are of principal interest for practice.
The location of the energy levels of rare-earth (RE) elements in the energy band diagram of BaF2 and CdF2 crystals is determined. The role of RE3+ and RE2+ ions in the capture of charge carriers, luminescence, and the formation of radiation defects i s evaluated. It is shown that the substantial difference in the luminescence properties of BaF2:RE and CdF2:RE is associated with the location of the excited energy levels in the band diagram of the crystals.
The spectral--kinetic characteristics of a ZnO:Ga single crystal upon excitation in the vacuum UV region have been studied. At a temperature of 8 K, the exciton luminescence line peaking at 3.356 eV has an extremely small half-width (7.2 meV) and a s hort decay time (360 ps). In the visible range, a wide luminescence band peaking at ~2.1 eV with a long luminescence time at 8 K and a decay time in the nanosecond range at 300 K is observed. The luminescence excitation spectra of ZnO:Ga have been measured in the range from 4 to 12.5 eV
The spectral characteristics of ZnO:Ga and ZnO:Ga,N ceramics prepared by uniaxial hot pressing have been investigated. At room temperature, the edge (exciton) band at 3.12 eV dominates in the luminescence spectra of ZnO:Ga, while a wide luminescence band at 2.37 eV, which is likely to be due to zinc vacancies, is observed in the spectra of ZnO:Ga,N. Upon heating, the edge band maximum shifts to lower energies and the bandwidth increases. The extrapolated position of the edge-band maximum at zero temperature, Em(0) = 3.367 +/- 0.005 eV, is in agreement with the data for thin zinc oxide films. The luminescence excitation spectra in the range from 3 to 6.5 eV are reported and the mechanism of energy transfer to excitons and luminescence centers is considered.
Ceramics ZnO:Zn of 20mm diameter and 1.6mm thickness with an optical transparency up to 0.33 in the visible region have been prepared by hot pressing technique. Scintillating and luminescent characteristics such as emission spectra, decay time, yield , and TSL glow curve have been measured under X-ray excitation. Two emission bands peaking at 500 and 380 nm were detected, the light output was about 80% of that for standard BGO scintillator, main decay constant was 10.4 +/- 0.1 ns. The obtained data allow us to consider the ZnO:Zn ceramics as a perspective scintillator. Finally, the investigation shows that other ZnO-based fast scintillators can be fabricated in the form of optical ceramics.
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