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Zhuravleva, Mariya

Publications and source records attributed to Zhuravleva, Mariya.

Intrinsic scintillation performance & europium concentration effects in RbSr 2 I 5 and RbSr 2 Br 5 scintillators

Scintillators play crucial roles in homeland security applications like gamma ray spectroscopy and high energy X-ray radiography. For promising new scintillators, fine-tuning the luminescent dopant concentration is one avenue to further improve their performance and tailor their properties. In this work, the effects of europium dopant concentrations on the crystal growth, luminescence and scintillation properties of RbSr 2 Br 5 and RbSr 2 I 5 crystals was investigated. Nine transparent 7 mm diameter single crystals were grown via the Vertical Bridgman method. Here, the optical band gap of RbSr 2 Br 5 was 5.9 eV and that of RbSr 2 I 5 was 4.7 eV. High scintillation performance was achieved with a relatively low europium concentration of 1 mol%. For both RbSr 2 Br 5 :Eu and RbSr 2 I 5 :Eu crystals, light yield of 60–90,000 ph/MeV, energy resolution 2.8–4.0 % at 662 keV, and X-ray afterglow 0.79–1.5 % at 2 ms were obtained.

36 MATERIALS SCIENCE↗

Impurity-enhanced core valence luminescence via Zn-doping in cesium magnesium chlorides

Scintillators with faster timing capabilities are currently in high demand for use in radiation detection systems in the fields of nuclear and medical physics. The limited number of suitable materials that meet the performance criteria of next generation detection systems presents an opportunity for discovery of new fast scintillator materials. In this work, the effects of doping several ultrafast core-valence luminescent (CVL) scintillators with divalent Zn is explored. Three compounds are investigated – CsMgCl 3 , Cs 2 MgCl 4 , and Cs 3 MgCl 5 – and single crystals of each doped with 5 mol% Zn are grown via the Bridgman method. Additionally, mixing across the full range of concentrations (from 0 % to 100 % Zn) is explored in the Cs 2 Mg 1-x Zn x Cl 4 and Cs 3 Mg 1-x Zn x Cl 5 systems. For low concentrations of Zn, light yields of all three compounds are enhanced (by up to ~60 %) compared to the pure crystals, achieving what we believe to be the brightest known CVL, CsMgCl 3 :Zn 5 % (3400 ± 170 ph/MeV light yield). More importantly, Zn doping does not affect the ultrafast timing properties, with each composition maintaining a single-component decay time around 1–3 ns. A sub-100 ps coincidence time resolution (CTR) is also achieved with CsMgCl 3 :Zn 5 %. The results of this work reveal a new avenue towards obtaining brighter CVL materials, which could open up possibilities for more advanced ultrafast scintillators to be discovered moving forward.

36 MATERIALS SCIENCE↗

Crystal growth, physical and optical properties of TlSr 2 Cl 5 and TlSr 2 Br 5

Small diameter (Ø 16 mm) TlSr 2 Cl 5 and TlSr 2 Br 5 crystals were grown by the Vertical Bridgman method. X-ray diffraction measurements show that both have the monoclinic crystal structure with space group P21/c. TlSr 2 Cl 5 and TlSr 2 Br 5 have a density of 4.14 g/cm 3 and 5.03 g/cm 3 , respectively. The effective Z of TlSr 2 Cl 5 and TlSr 2 Br 5 is 63.7 and 58.6, respectively. Radioluminescence spectra of TlSr 2 Cl 5 and TlSr 2 Br 5 feature a broad emission band peaking at 440 and 445 nm, respectively. As a result the light yield of TlSr 2 Cl 5 and TlSr 2 Br 5 was estimated to be 17,000 and 45,000 ph/MeV, respectively.

36 MATERIALS SCIENCE↗

New Ultrafast Scintillators with Core Valence Luminescence: Cs 2 MgCl 4 and Cs 3 MgCl 5

Future experiments in high energy physics and medical imaging require radiation detectors having properties which are not presently available. The main limitations arise from lack of suitable scintillation crystals. This dilemma prompts the need for research leading to the discovery of new fast and bright scintillator materials that combine unique properties to fulfil modern experiment requirements without compromises. In this work, single crystals of Cs 2 MgCl 4 and Cs 3 MgCl 5 up to 12 mm in diameter are grown via the vertical Bridgman method. Scintillation properties are reported for the first time, and core valence luminescence is observed for both compounds. X-ray excited radioluminescence emission of Cs 2 MgCl 4 is centered at 295 nm, with a scintillation decay time of 2.25 ± 0.05 ns and relatively high core-valence light yield of 2,200 ± 110 ph/MeV. Cs 3 MgCl 5 has two main emission peaks centered at 242 nm and 302 nm, decay time of 1.46 ± 0.05 ns, and light yield of 1,340 ± 70 ph/MeV. The better coincidence time resolution (CTR) is obtained with Cs 2 MgCl 4 , which is measured to be 129 ± 4 ps FWHM. Density functional theory (DFT) calculations are also performed and provide supporting evidence that the observed scintillation originates from core valence luminescence. Furthermore, the combination of speed and brightness of these new scintillators could be useful for fast timing applications in which moderately dense materials are required.

36 MATERIALS SCIENCE↗

Crystal growth of new high light yield halide perovskite scintillator RbSrI 3

X-ray radiography systems are a key national security technology enabling non-invasive cargo screening. However, the scintillators currently used in these systems have limitations in performance that prompt research for new suitable materials. Here, in this work, crystal growth, physical properties, and optical and scintillation properties of a new halide perovskite scintillator RbSrI 3 were investigated for the first time. The melting point was determined to be 453 °C. Divalent europium and ytterbium were investigated as potential luminescent activators. Light yield and energy resolution of RbSrI 3 :Eu 5 mol% was 78,700 ph/MeV and 2.8 % at 662 keV, and that of RbSrI 3 :Yb 0.5 mol% was 24,000 ph/MeV and 4.9 % at 662 keV.

36 MATERIALS SCIENCE↗

Crystal Growth and Characterization of Europium-Doped Rubidium Calcium Bromide Scintillators

National security strategies like gamma spectroscopy and high-energy X-ray radiography are limited, in part, by the scintillator used, prompting research into novel materials with improved properties. In this paper, Eu 2+ activated rubidium calcium bromide scintillators were grown via the vertical Bridgman method with a range of dopant concentrations. Light yield, energy resolution, and the afterglow of Rb 4 CaBr 6 :Eu and RbCaBr 3 :Eu improved with increasing Eu 2+ concentration, and scintillation decay time increased. The highest light yields of Rb 4 CaBr 6 :Eu and RbCaBr 3 :Eu were 71000 and 45000 ph/MeV, respectively.

36 MATERIALS SCIENCE↗

Serrated flow in $\mathrm{NaI:Tl}$ scintillator crystals

We report the serrated-flow behavior is an important phenomenon that unveils material-deformation mechanisms, as reported for various kinds of materials. NaI doped with Tl (NaI:Tl) is unique among scintillation materials in that the structure contains glide planes that are linked to serration behavior. In the present work, single crystals of NaI:Tl were subjected to room-temperature compression experiments at different strain rates. The serrated flow was observed, and complexity and multifractal analyses were performed to analyze the serration behavior. The findings revealed that the strain rate had a pronounced effect on the complexity and multifractality of the serrated flow, similar to what has been found in other alloy systems. The results also indicate that there may be a strong link between the complexity of the serrated flow behavior and the heterogeneity of the underlying dynamics. It is expected that the present work could be a step toward a better understanding of the deformation behavior and forgeability of NaI:Tl single crystals.

36 MATERIALS SCIENCE↗

In Situ High-Temperature Structural Analysis of High-Entropy Rare-Earth Sesquioxides

High-entropy rare-earth (RE) sesquioxides (RE 2 O 3 ) containing five cations in equimolar amounts have been investigated for a variety of applications, but little is known about their polymorphic behavior and coefficient of thermal expansion. Here, in this work, we evaluate the effect of the average ionic radius (AIR) on the polymorphism of high-entropy RE 2 O 3 . Powder samples of compositions 1 (Lu,Y,Ho,Nd,La) 2 O 3 (AIR = 0.938 Å) and 2 (Gd,Eu,Sm,Nd,La) 2 O 3 (AIR = 0.982 Å) were synthesized via a wet chemical method, and bead samples were prepared for aerodynamic levitation by melting the powders in a copper hearth. Structural transitions were monitored upon cooling from the melt to 1000 °C via in situ X-ray diffraction on aerodynamically levitated samples. The phase evolution was liquid, hexagonal H-type, and monoclinic B-type for composition 1 and liquid, cubic X-type, H-type, and B-type for composition 2. Based on their AIR, the general polymorphic transformations of the high-entropy RE 2 O 3 follow the trend of single-RE RE 2 O 3 , but the transition temperatures differ from those of single-RE RE 2 O 3 . The coefficient of thermal expansion values of the B-type phase of compositions 1 and 2 are similar to those of Gd 2 O 3 and previously published high-entropy RE 2 O 3 .

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Crystal Growth and Phase Formation of High-Entropy Rare-Earth Aluminum Perovskites

In this work, we demonstrate for the first time the crystal growth of high-entropy rare-earth (RE) aluminum perovskites (REAlO 3 ) using the micro-pulling-down method to inform future exploration of functional crystals. To determine how composition affects phase formation, we formulate equiatomic compositions containing five REs from the following list: Lu, Yb, Tm, Er, Y, Ho, Dy, Tb, Gd, Eu, Sm, Nd, Pr, Ce, La. To test whether combinations of REs with similar ionic radii may favor a single phase, compositions containing REs with consecutive or nonconsecutive ionic radius values were formulated. Powder and single-crystal X-ray diffraction indicate that crystals containing only REs with similar ionic radii that form orthorhombic single-RE REAlO 3 are a single phase. Crystals containing REs with dissimilar ionic radii or mixtures of REs that form orthorhombic, rhombohedral, and tetragonal single-RE REAlO 3 are a mixture of phases. The elemental distribution in single-phase crystals analyzed via electron probe microanalysis confirms no evidence of preferential incorporation of any of the constituent REs. The distribution and composition of secondary phases were analyzed via scanning electron microscopy and energy dispersive spectroscopy; secondary phases were seen as a small region in the center of the crystals with branching features closer to the outer surface.

36 MATERIALS SCIENCE↗

Tuning the melting point and phase stability of rare-earth oxides to facilitate their crystal growth from the melt

The challenge of growing rare-earth (RE) sesquioxide crystals can be overcome by tailoring their structural stability and melting point via composition engineering. This work contributes to the advancement of the field of crystal growth of high-entropy oxides. A compound with only small REs (Lu,Y,Ho,Yb,Er) 2 O 3 maintains a cubic C-type structure upon cooling from the melt, as observed via in-situ high-temperature neutron diffraction on aerodynamically levitated samples. On the other hand, a compound with a mixture of small and large REs (Lu,Y,Ho,Nd,La) 2 O 3 crystallizes as a mixture of a primary C-type phase with an unstable secondary phase. Crystals of compositions (Lu,Y,Ho,Nd,La) 2 O 3 and (Lu,Y,Gd,Nd,La) 2 O 3 were grown by the micro-pulling-down (mPD) method with a single monoclinic B-type phase, while a powder of (Lu,Y,Ho,Yb,Er) 2 O 3 did not melt at the maximum operating temperature of an iridium-rhenium crucible. The minimization of the melting point of the two grown crystals is attributed to the mismatch in cation sizes. The electron probe microanalysis reveals that the general element segregation behavior in the crystals depends on the composition.

36 MATERIALS SCIENCE↗

Improved light yield and growth of large-volume ultrafast single crystal scintillators Cs 2 ZnCl 4 and Cs 3 ZnCl 5

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 mm 3 and 7 × 7 × 10 mm 3 pixels cut from Ø22 mm Cs 2 ZnCl 4 are measured to be 148 ± 1 ps FWHM and 175 ± 1 ps FWHM, respectively. Here, 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.

36 MATERIALS SCIENCE↗

Effects of composition and growth parameters on phase formation in multicomponent aluminum garnet crystals

The effects of com­position on the phase formation of multicom­ponent garnet crystals grown via directional solidification by the micro-pulling-down method are studied. A relatively wide range of rare-earth (RE) average ionic radii (AIR) is explored by formulating ten com­positions from the system (Lu,Y,Ho,Dy,Tb,Gd) 3 Al 5 O 12 . Crystals were grown at either 0.05 or 0.20 mm min -1 . The hypothesis is that multicom­ponent com­pounds with large AIR will form secondary phases as the single-RE aluminum garnets formed by larger Tb 3+ or Gd 3+ ; this will result in crystals of poor optical quality. Crystals with large AIR have a central opaque region in optical microscopy images, which is responsible for their reduced transparency com­pared to crystals with small AIR. Slow pulling rates suppress the formation of the opaque region in crystals with inter­mediate AIR. Powder and single-crystal X-ray diffraction and electron probe microanalysis results indicate that the opaque region is a perovskite phase. Scanning electron microscopy and energy dispersive spectroscopy measurements reveal eutectic inclusions at the outer surface of the crystals. Finally, the concentration of the eutectic inclusions increases with increasing AIR.

36 MATERIALS SCIENCE↗

Tl+-based and mixed halide A3B2X9-type scintillators

Inorganic halides (e.g., inorganic halide scintillators) of the general formula A3B2X9, including inorganic halides comprising thallium monovalent cations and/or combinations of different halides, are described. Radiation detectors including the inorganic halide scintillators and methods of using the detectors to detect high energy radiation are also described. In some cases, the scintillators can include a gadolinium cation, a boron cation, a lithium cation, a chloride ion, or combinations thereof and the scintillator can be used to detect neutrons.

Rutstrom, Daniel↗