1. Managed by UT-Battelle for the U.S. Department of Energy Novel Materials for Radiation Detection: Transparent Ceramics and Glass Scintillators Lynn A. Boatner Oak Ridge National Laboratory Center for Radiation Detection Materials & Systems 2008 AAAS Annual Meeting February 16, 2008

2. 2 Managed by UT-Battelle for the U.S. Department of Energy Overview_0704 Scintillators: A Little History Barium platinocyanide is considered to be the first radiation detector. The scintillation from a screen of platinocyanide alerted Wilhelm Röntgen to the presence of some strange radiation emanating from a gas discharge tube he was using to study cathode rays. Since Röntgen did not know what these “rays” were, he named them x-rays. Wilhelm Conrad RöntgenBarium Platinocyanide purchased in the late 1800’s by Sidney Rowland, King’s College, London

3. 3 Managed by UT-Battelle for the U.S. Department of Energy Overview_0704 Scintillators: A Little History This radiographic image was formed by placing the barium platinocyanide on a photographic film. The reason for this effect is that the state of separations chemistry in the 1800’s was poor and the barium platinocyanide was contaminated by radium. G. Brandes found that sufficiently energetic x-rays produced a uniform blue-grey glow that seemed to originate within the eye itself. Friedrich Giesel (Curie) “saw” radiation from radium “to obtain this effect, one places the box containing the radium in front of the closed eye or against the temple" and "one can attribute this phenomenon to a phosphorescence in the middle of the eye under the action of the invisible rays of radium" (Curie 1900, 1903). In the United States, the Colorado physician George Stover5 was among the first investigate radiation phosphenes (the proper name for visual sensations induced by radiation within the eye): "Sitting in a perfectly dark room and closing the eyes, if the tube of radium is brought close to the eyelids a sensation of light is distinctly perceived, which disappears on removal of the tube...”

4. 4 Managed by UT-Battelle for the U.S. Department of Energy Overview_0704 State of the Art Scintillators MaterialLight Yield (photons/MeV) Resolution @ 662keV (%) NaI(Tl)38,0005.5 BGO8,2009.0 LaBr 3 (Ce)70,0002.8 LSO(Ce)39,0007.9 BC-408 Plastic10,600- GS-20 Li Glass ($2930 for 1-inch round, 2mm thick/ $4,739 for 6.2-inch square, 2mm thick plate) 4,10017

5. 5 Managed by UT-Battelle for the U.S. Department of Energy Overview_0704 Transparent Polycrystalline Ceramic Scintillators Glass Scintillators Why would we want these?  Single crystal growth is a time-consuming, expensive, and rate- limiting process.  Transparent polycrystalline ceramic scintillators and glass scintillators offer an alternative approach to scintillator synthesis that eliminates single crystal growth.

6. 6 Managed by UT-Battelle for the U.S. Department of Energy Overview_0704 Oak Ridge National Laboratory-Transparent Polycrystalline Scintillators Conceptual Overview: The Realization of an Entirely New Paradigm for the Fabrication of Inorganic Scintillators — Specifically, an approach that is applicable to non-cubic as well as cubic materials–– Through the development of versatile methods for producing large, optically transparent, high-performance (resolution, light yield, decay time,) inorganic scintillators without the necessity of growing large single crystals. Accomplish this goal by applying the concept of developing highly crystallographically oriented (highly textured) ceramic microstructures1,2 –– So that the material looks like a single crystal from the crystallographic point of view, and therefore, light scattering due to the effects of birefringence of the randomly oriented grains in a conventional ceramic is obviated. 1.L. A. Boatner, J. L. Boldú, and M. M. Abraham, “Characterization of Textured Ceramics by Electron Paramagnetic Resonance Spectroscopy: I, Concepts and Theory,” J. Am. Ceram. Soc. 73, (8) 2333–2344 (1990). 2.J. L. Boldú, L. A. Boatner, and M. M. Abraham, “Characterization of Textured Ceramics by Electron Paramagnetic Resonance Spectroscopy: II, Formation and Properties of Textured MgO,” J. Am. Ceram. Soc. 73, (8) 2345–2359 (1990)

7. 7 Managed by UT-Battelle for the U.S. Department of Energy Overview_0704 Why is it important to develop methods for forming transparent ceramic scintillators of non-cubic materials? The current scintillators with the highest energy resolution (LaBr 3 :Ce at ~2.6%) or very high light yield (LuI 3 :Ce at 100,00 photons/Mev) are not cubic materials. There are a lot more non-cubic materials than there are cubic materials. The technology for forming transparent ceramics of cubic materials is already well developed for a number of materials (e.g. YAG and related materials) as a result of Japanese research on polycrystalline laser rods. The claims that transparent ceramics can only be made with cubic materials is WRONG! Transparent HAp sintered body fabricated by PECS. (2.0 cm O.D., 1 mm thick) Ca 10 (PO 4 ) 6 (OH) 2 A hexagonal (NOT CUBIC) crystal XRD patterns of the sintered HAp body measured on the sections parallel (a) and perpendicular (b) to the pressure direction. Transparent polycrystalline ceramic prepared by developing a high degree of texturing. Y. Watanabe, et all, J. Am. Ceram. Soc., 88 [1] 243-5 (2005) Oak Ridge National Laboratory-Transparent Polycrystalline Scintillators

8. 8 Managed by UT-Battelle for the U.S. Department of Energy Overview_0704 Project Objectives:  Develop New Densification Techniques for Producing Optically Transparent, Highly Textured Inorganic Scintillators––of both non-cubic and cubic materials  At reduced cost  At increased production rates  Eliminate single crystal growth  Minimize fabrication steps –near-net shape ceramics  Maintain scintillator performance Key Research:  Hot pressing and annealing  Vacuum sintering  Precursor Development  Post Sintering Processing  Scintillator Characterization Lu 2 O 3 : 5%Eu 2 O 3 Transparent Ceramics Hot pressed at 1520 ºC, 321 kg/cm 2 for 2 hrs Project Objectives and Key Research

9. 9 Managed by UT-Battelle for the U.S. Department of Energy Overview_0704 Photograph of a Lu 2 O 3 :Eu ceramic excited by a 30kV continuous X-ray source. Lu 2 O 3 :Eu Synthesis and Post Synthesis Treatment Lu 2 O 3 and Eu 2 O 3 (5 wt. %) powders combined physically Powder heated in vacuum to dry Hot pressed at 1530 ° C with 262 kg/cm 2 of pressure Annealed with flowing oxygen for 72 hours at 1050 ° C Photographs of a transparent Lu 2 O 3 :Eu ceramic (~1mm thick) Photograph of a Lu 2 O 3 :Eu ceramic before (right) and after (left) annealing in an oxygen atmosphere. Hot pressing technique tends to draw oxygen out of the host lattice, creating a dark color in the densified body. This coloration can be removed by annealing in an O 2.

10. 10 Managed by UT-Battelle for the U.S. Department of Energy Overview_0704 LSO:Ce Synthesis and Post-synthesis Treatment High quality LSO:Ce powder produced by Nichia Corporation (Japan) used Powder heated in vacuum to dry Hot pressed at 1400 ° C with 337 kg/cm 2 of pressure for 2 hours Annealed in vacuum at 1050 ° C/108h Annealed in water vapor at 1050 ° C/32h Annealed in air at 1150 ° C/32h Photograph of a LSO:Ce ceramic before (left) and after (right) annealing in vacuum Photograph of an LSO:Ce ceramic (0.6 mm thick). Note that no back- light is used in this photograph. Scanning electron microscopy (SEM) image of LSO:Ce powder from Nichia Corporation. Transmission electron microscopy (TEM) image of LSO:Ce powder from Nichia Corporation Particle size distribution of the Nichia LSO:Ce powder used to make the LSO ceramic.

11. 11 Managed by UT-Battelle for the U.S. Department of Energy Overview_0704

12. 12 Managed by UT-Battelle for the U.S. Department of Energy Overview_0704 X-ray pole figure for LSO:Ce ceramic showing no evidence for texturing in the ceramic microstructure. X-ray diffraction Θ-2Θ scan for the LSO:Ce ceramic with the standard powder diffraction pattern.

13. 13 Managed by UT-Battelle for the U.S. Department of Energy Overview_0704 Scintillating pulse shape of a LSO:Ce polycrystalline ceramic excited by 662 KeV gamma photons. The solid line represents single- and three-exponential (+ noise) fits to the experimental data. The decay time constants and contribution of faster components in comparison to the decay time of about 42 ns generally accepted for single crystal LSO. Energy spectra (for 662 keV excitation photons) of the LSO:Ce refernce crystal (the light yield for this crystal was ~30,000 photons/MeV) and the LSO:Ce ceramic at various post-sintering annealing stages. Symbol “A” denotes a ceramic with a 2 mm thickness after annealing in vacuum, “A1” denotes a 0.7 mm thick piece of the former ceramic after additional annealing in water vapor, and “A1a” the same after additional annealing in air.

14. 14 Managed by UT-Battelle for the U.S. Department of Energy Overview_0704 LaBr 3 :Ce Synthesis and Post-synthesis Treatment LaBr3 and CeBr3 (2 wt. %) powders combined manually Powder heated at 350 ° C/24 in vacuum to dry Hot pressed under vacuum at 780 ° C with 388kg/cm 2 of pressure for 3 hours. Annealed in vacuum at 650 ° C/24h Photograph of a translucent LaBr 3 :Ce ceramic scintillator (-0.7 mm thick). Illumination circle is about 2.5 cm in diameter.

15. 15 Managed by UT-Battelle for the U.S. Department of Energy Overview_0704 Energy spectra of a BGO reference crystal and the LaBr 3 :Ce (2%) ceramic for several excitation energies.

16. 16 Managed by UT-Battelle for the U.S. Department of Energy Overview_0704 Novel Cerium-Activated Phosphate Glass Scintillators IR Phosphors Linda Lewis Gamma, X-Ray, and Neutron Scintillators Lynn Boatner and John Neal Modeling David Singh Phosphate Glass

17. 17 Managed by UT-Battelle for the U.S. Department of Energy Overview_0704 Research Goals & Objectives  Research Goals: To exploit the chemical flexibility, optical properties, and the unusual structural features and variability of the ORNL phosphate glasses and other glass systems in order to develop a new glass scintillator with significantly improved radiation-detection (i.e., light yield) characteristics.  Applications: Glass scintillators can be easily and economically fabricated in the form of large structures (e.g., as large area plates, tubes, rods, or bars) or pulled into optical fiber structures with wave-guiding properties.  As a result of their thermal, mechanical and chemical durability, glass scintillators are ideal for use as radiation detectors in devices that have to operate in the field under a variety of frequently adverse conditions. High Durability Lead Scandium Phosphate Glasses Nd-doped phosphate glasses known to be effective phosphors when excited by IR

18. 18 Managed by UT-Battelle for the U.S. Department of Energy Overview_0704 Glass Scintillators: How Can We Improve Their Performance? Glass Scintillator Parameter Space Composition (Glass-forming space) Cladding Phosphate Lead Phosphate Silicate Germanate Arsenate … Activation Ce,Pr,Nd,Eu,Tb,Yb Co-doping Post-synthesis Treatment Time Temperature Atmosphere Structure Phosphate glass only Phosphate chain length

19. 19 Managed by UT-Battelle for the U.S. Department of Energy Overview_0704 Phosphate Glass - Gamma and X-ray Scintillators Retort for variations of synthesis routes for introducing Ce 3+ and maintaining it in the trivalent state. UV Excitation LuPbPO 4 :Eu ScPbPO 4 :Eu Ce 3+ valence can be a challenging problem - partially solved for silicate glasses, needs to be solved for phosphate and other glasses.

20. 20 Managed by UT-Battelle for the U.S. Department of Energy Overview_0704 137 Cs 1μCi γ source 662 keV γ photons 0.5 μs shaping time Energy Spectra of Ce Doped Ca-Na Phosphate Glasses

21. 21 Managed by UT-Battelle for the U.S. Department of Energy Overview_0704 Variation Of Compton Edge Position as a Function of Ce Concentration in Ca-Na Phosphate Glass

22. 22 Managed by UT-Battelle for the U.S. Department of Energy Overview_0704 Comparison of Energy Spectra 137 Cs 1μCi γ source 662 keV γ photons 0.5 μs shaping time

23. 23 Managed by UT-Battelle for the U.S. Department of Energy Overview_0704 Effects of Na Substitution By Li And Gd Co-doping in Li-Ca Glass

24. 24 Managed by UT-Battelle for the U.S. Department of Energy Overview_0704 Key General Objectives and Goals Develop new glass scintillator systems through the exploration of compositional variations in phosphate, silicate, germanate, arsenate and other glass-forming systems. Explore the effects of post-synthesis treatments (i.e., thermochemical processing) on glass scintillator properties. Investigate the performance of activators other than cerium in various glass host systems. Investigate energy transfer processes in glasses as a function of the material’s structure (amorphous versus crystalline materials) and electronic properties. – Variable temperature studies – Identification of luminescence centers, impurities, defects, etc – Relative position of luminescence center levels in the bandgap of the host – Idendtify mechanisms that delay the transfer of energy to luminescence centers Apply this increased understanding to the synthesis of glass scintillators with improved performance characteristics.