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Payne, S. A.

Publications and source records attributed to Payne, S. A..

3D printed transparent ceramic YAG laser rods: Matching the core-clad refractive index

Yttrium Aluminum Garnet (YAG) solid state laser gain media rods with an active Neodymium-doped core and an optically-clear cladding region were additively manufactured via direct-ink-writing (DIW), followed by sintering and hot isostatic pressing to form fully dense optical ceramics. Lutetium and Gadolinium were chosen as optically-inert co-doping ions in the clad to match the increase in refractive index caused by the Neodymium in the core. Additionally, either 11.6% Lutetium or 3.8% Gadolinium can be used to match the index change from 2% neodymium; however, differences in diffusion distances across the core-clad interface lead to large fluctuations in index in that region. These index fluctuations can be minimized either by matching dopants with similar diffusion distances, or by implementing a gradual gradient in the doping profile, possible through DIW, rather than a sharp compositional interface attainable via more standard fabrication methods. This improvement in index homogeneity resulted in a 40% improvement in lasing performance compared with that of a core-clad rod fabricated with a sharp interface between the doped and undoped regions.

36 MATERIALS SCIENCE↗

Multiple dye interactions in plastic scintillators: Effects on pulse shape discrimination

The scintillation process in plastic scintillators has been studied with mixed systems containing high concentrations of multiple fluorescence dyes. It has been shown that the triplet–triplet interaction phenomena leading to the production of delayed light and pulse shape discrimination (PSD) can vary depending on the triplet energies of the interacting dyes. At small differences between the first excited triplet state energies, found to be below 0.1 eV, a pair of interacting dyes of different molecular species can be involved in heterogeneous excitation migration and triplet–triplet annihilation that result in the enhancement of delayed light and PSD, due to the engagement of both dyes in the process. At differences above 0.27 eV, excitation trapping on the lower energy triplet molecules leads to conditions when triplet–triplet migration and annihilation can proceed only homogeneously between molecules of the same species. The results explain the different effects produced by the selection of fluorescent dyes in previously reported PSD systems containing one primary and one secondary dyes. They also demonstrate a non-traditional approach to the design of new plastic scintillators with multiple dyes that, at improved scintillation and PSD performance, may simplify the production process.

36 MATERIALS SCIENCE↗

Plastic scintillators stable for operating in wide ranges of humidity and temperature variations

To provide efficient and reproducible response to nuclear radiation, scintillating plastics should be prepared as materials of high optical transparency and homogeneity that should remain intact during the lifetime of their operation. A problem with traditionally used polyvinyltoluene (PVT) or polystyrene (PS) plastic scintillators arises from their exposure to repeated large temperature swings that cause surface and volume defects, resulting in decreased sensitivity of the detection properties. We find that the problem can be avoided by composition modifications that enable preparation of plastics with properties that are resistant to the continuous variations in environmental conditions. This paper describes improvements in physical properties that can be achieved by the addition of crosslinkers (such as divinylbenzene, DVB) and oxygen-containing compounds or copolymers (e.g. polymethylamethacrylate, PMMA) to the traditional PVT or PS polymer matrices. Results of characterization show that the new materials can be prepared with the scintillation performance equal to that of commercial plastic scintillators, such as EJ-200.

36 MATERIALS SCIENCE↗

Luminescence of Mn 4+ in the Orthorhombic Perovskites, ASnO 3 (A=Ca, Sr)

The aim of this paper is to provide a comparative study of the spectroscopic properties of Mn 4+ (3 d 3 ) ion in the orthorhombic perovskites, ASnO 3 (A=Ca, Sr). The most significant parameter controlling the energy of the zero-phonon line ( 2 E→ 4 A 2 transition) is the deviation of the octahedral O-Mn-O bond angle from the ideal 90 0 value. It is significant that despite the longer Sn 4+ -O 2- bond distance, the crystal field strength (10 D q ) in CaSnO 3 is higher than that of SrSnO 3 . We discuss this result in relation to the perovskite crystal chemistry. Mulliken population analysis and bond order calculation are made to clarify the nature of chemical bonding in the stannate perovskites.

36 MATERIALS SCIENCE↗

Optical spectrum of Mn 4+ in Y 2 Ti 2-x Sn x O 7 pyrochlore solid solution: R-line energy and intensity

We report we investigated the luminescence of the Mn 4+ ions in Y 2 Ti 2-x Sn x O 7 (x = 0, 0.5, 1.0, 2.0) pyrochlore solid solutions and compared the results with the spectroscopic data of the two end members. The emission spectra in the mixed pyrochlore solid solutions are broadened relative to the end members due to long range disorder between the Sn 4+ and Ti 4+ ions. The R-line intensity is particularly weak in both Y 2 Sn 2 O 7 and Y 2 Ti 2 O 7 . The increase in R-line intensity in the mixed pyrochlore solid solutions is attributed to the random distribution of Sn 4+ and Ti 4+ ions in the second coordination sphere (next nearest neighbors) that removes the inversion symmetry about the Mn 4+ ion. We find a linear relation between the energy position of the R-line and x in Y 2 Ti 2-x Sn x O 7 ( 2 E g (cm –1 ) = 15 010 + 163.0 x; R 2 = 0.98).

36 MATERIALS SCIENCE↗

On the Mn 4+ R-line emission intensity and its tunability in solids

The spectroscopic properties of Mn 4+ ions in solids are analyzed to establish key parameters that are responsible for the energy and the intensity of the 2 E g → 4 A 2g zero-phonon emission transition (R-line). These two factors of the emission spectrum are critical in determining the phosphor luminosity or brightness. The emission energy is chiefly determined by the “Mn 4+ -ligand” bonding covalence. In fluorides, the Mn-F bonding covalence is weak, and the R-line occur at higher energy. In oxides, the stronger Mn-O bonding covalence reduces the energy of the 2 E g state. In oxides, the R-line shifts to higher energy with increasing local distortion of the MnO 6 octahedral moiety. Those host crystals that locate the Mn 4+ ion at a noncentrosymmetric site (absence of inversion symmetry) relax the parity section rule, which enhances the R-line intensity. Increased R-line intensity in the emission spectrum produces color changes that increases phosphor luminosity. The influence of second coordination sphere (next-nearest neighbors) on the R-line intensity is considered. This article establishes guidelines for the development of host crystals that meet the requirements of high luminosity phosphors for general illumination applications.

36 MATERIALS SCIENCE↗

Spectroscopy of Mn 4+ in orthorhombic perovskite, LaInO 3

The low temperature spectroscopic properties of Mn 4+ (3d 3 ) in the orthorhombic perovskite, LaInO 3 , is examined in this work. The exchange charge model of crystal-field theory is used to calculate the Mn 4+ energy levels. The spectra can be fitted by the parameters D q = 1776 cm –1 , B = 700 cm –1 and C = 3189 cm –1 , with C/B = 4.5. Discussions pertaining to the low luminescence efficiency of LaInO 3 :Mn 4+ are presented. A comparative study of the variations in the energy of the 2 E g → 4 A 2g emission transition in a series of materials with the perovskite structure is presented. Here, the data suggest a relationship between the energy of the 2 E g → 4 A 2g emission transition and the deviation of the octahedral O-Mn-O bond angle from the ideal 90°. It is concluded that the angular distortion is not large enough to support the development of high luminosity Mn 4+ activated phosphors in the ABO 3 perovskite family of materials.

36 MATERIALS SCIENCE↗

Ba(1-x)SrxMg3SiN4:Eu narrowband red phosphor

We evaluated polyvinyl toluene (PVT) scintillators fabricated with different emitting dopants and scintillator optical configurations for fast neutron imaging. A neutron imaging apparatus was constructed to study scintillators under MeV neutron exposure. PVT with 2% Xylyl Flrpic emitter was identified as the brightest. The addition of a black backing to the scintillator, compared with a specular reflector film backing, improved the resolution of the neutron image obtained with the PVT scintillator by about 2 9. It is concluded that a PVT imaging screen with 2% Xylyl Flrpic, configured with a black backing, provides the best quality fast neutron image of the scintillators tested.

Osborne, R. A.↗

Solution growth of a deuterated trans -stilbene crystal for fast neutron detection

The paper reports results on growth and characterization of the first deuterated analog of the trans -stilbene crystal. The high optical quality stilbene-d12 single crystal was grown by application of the solution technique using specially synthesized raw material and an aromatic solvent (anisole). Optical, physical, and scintillation properties of the new material are compared to those of the regular trans -stilbene crystal. In conclusion, the new deuterated material is promising for use in fast neutron spectroscopy without the need for time-of-flight measurements.

36 MATERIALS SCIENCE↗

Recent developments in plastic scintillators with pulse shape discrimination

The paper reports results of studies conducted to improve scintillation performance of plastic scintillators capable of neutron/gamma pulse-shape discrimination (PSD). Compositional modifications made with the polymer matrix improved physical stability, allowing for increased loads of the primary dye that, in combination with selected secondary dyes, provided enhanced PSD especially important for the lower energy ranges. Additional measurements were made with a newly-introduced PSD plastic EJ-276, that replaces the first commercially produced EJ-299. Comparative studies conducted with the new materials and EJ-309 liquids at large scale (up to 10 cm) show that current plastics may provide scintillation and PSD performance sufficient for the replacement of liquid scintillators. In conclusion, comparison to stilbene single crystals compliments the information about the status of the solid-state materials recently developed for fast neutron detection applications.

36 MATERIALS SCIENCE↗

Increased fluorescence intensity in CaTiO 3 :Pr 3+ phosphor due to NH 3 treatment and Nb Co-doping

Development of next generation red phosphors for commercial lighting requires understanding of how increased luminescence is achieved by various treatment strategies. In our work, we compare co-doping with Nb to NH 3 treatment of CaTiO 3 :Pr phosphors to reveal a general mechanism responsible for the increased luminescence. The phosphors were synthesized using standard solid-state synthesis techniques and the fluorescence was characterized for potential use in fluorescent lighting, with 254 nm excitation. The lifetime of the fluorescence was determined and used to identify a change in a trap state by the co-doping of Nb 5+ in the phosphor. Furthermore, the oxidation state of the Pr was probed by NEXAFS and revealed that both Nb 5+ co-doping and NH 3 treatment reduced the number of non-fluorescing Pr 4+ centers. We performed calculations in order to determine the energetically favorable defects. Vacuum annealing was also used to further probe the nature of the trap state. It was determined that NH 3 treatments reduce the number of Pr 4+ non-fluorescing centers, while Nb 5+ co-doping additionally reduces the number of excess oxygen trap states that quench the fluorescence.

36 MATERIALS SCIENCE↗

Effect of chlorination on the TlBr band edges for improved room temperature radiation detectors: Effect of chlorination on the TlBr band edges for radiation detectors

Thallium bromide (TlBr) crystals subjected to hydrochloric acid (HCl) chemical treatments have been shown to advantageously affect device performance and longevity in TlBr-based room temperature radiation detectors, yet the exact mechanisms of the improvements remain poorly understood. Here in this paper, we investigate the influence of several HCl chemical treatments on device-grade TlBr and describe the changes in the composition and electronic structure of the surface. Composition analysis and depth profiles obtained from secondary ion mass spectrometry (SIMS) identify the extent to which each HCl etch condition affects the detector surface region and forms of a graded TlBr/TlBr 1-x CL x surface heterojunction. Using a combination of X-ray photoemission spectroscopy (XPS) and hybrid density functional calculations, we are able to determine the valence band offsets, band gaps, and conduction band offsets as a function of Cl content over the entire composition range of TIBr 1-x C1 X . This study establishes a strong correlation between device process conditions, surface chemistry, and electronic structure with the goal of further optimizing the long-term stability and radiation response of TlBr-based detectors.

36 MATERIALS SCIENCE↗

X-ray photoemission analysis of chemically modified TlBr surfaces for improved radiation detectors

We subjected device-grade TlBr to various chemical treatments used in room temperature radiation detector fabrication to determine the resulting surface composition and electronic structure. As-polished TlBr was treated separately with HCl, SOCl 2 , Br:MeOH and HF solutions. High-resolution photoemission measurements on the valence band electronic structure and Tl 4f, Br 3d, Cl 2p and S 2p core lines were used to evaluate surface chemistry and shallow heterojunction formation. Surface chemistry and valence band electronic structure were correlated with the goal of optimizing the long-term stability and radiation response.

36 MATERIALS SCIENCE↗

Cr(+2) Diffusion Doping in ZnSe

Chromium doped zinc selenides crystals have recently been demonstrated to be a promising material for near-IR room temperature tunable lasers which has an emission range of 2-3 pm. In this study, a new diffusion doping process has been developed for incorporation of Cr(+2) ion into ZnSe wafers. This process has been successfully performed under isothermal conditions, at temperatures above 800 degrees Celsius. Concentrations in excess of 10(exp 19) Cr(+2) ions/cu cm, an order of magnitude larger than previously reported in melt grown ZnSe material, have been obtained. The diffusivity was estimated to be about 10-* sq cm/sec using a classical diffusion model. Resistivity was derived from current-voltage measurements and in the 107-10(exp 16) Ohms-cm and increased as function of Cr concentration.

Journigan, Troy D.↗

Chromium Diffusion Doping on ZnSe Crystals

Chromium doped zinc selenide crystal have recently been demonstrated to be a promising material for near-IR room temperature tunable lasers which have an emission range of 2-3 micrometers. In this study a new diffusion doping process has been developed for incorporation of Cr(+2) ion into ZnSe wafers. This process has been successfully performed under isothermal conditions, at temperatures above 800 C. Concentrations in excess of 10(exp 19) Cr(+2) ions/cu cm, an order of magnitude larger than previously reported in melt grown ZnSe material, have been obtained by diffusion doping, as estimated from optical absorption measurements. The diffusivity was estimated to be about 10(exp -8) sq cm/sec using a thin film diffusion model. Resistivity was derived from current-voltage measurements and in the range of 10(exp 13) and 10(exp 16) omega-cm. The emission spectra and temperature dependent lifetime data will also be presented and discussed.

Journigan, Troy D.↗