Fracture-resistant lanthanide scintillators

• US 7,863,572 B1
• Filed: 07/17/2008
• Issued: 01/04/2011
• Est. Priority Date: 07/17/2007
• Status: Active Grant

• Current Assignee: National Technology & Engineering Solutions Of Sandia LLC (Honeywell International Inc.)
• Original Assignee: Sandia Corporation (Martin Marietta Corporation)
• Inventors: Doty, F. Patrick
• Primary Examiner(s): Porta; David P
• Assistant Examiner(s): Kim; Kiho
• Application Number:
  US12/174,761
• Time in Patent Office: 901 Days
• Field of Search: 250/361.R, 25037001-37015, 378/98.8, 252/301.17, 252/301.4 H
• US Class Current: 250/361.00R
• CPC Class Codes: G01T 1/2023 Selection of materials see provisionally also G01T1/202

Abstract

Lanthanide halide alloys have recently enabled scintillating gamma ray spectrometers comparable to room temperature semiconductors (<3% FWHM energy resolutions at 662 keV). However brittle fracture of these materials upon cooling hinders the growth of large volume crystals. Efforts to improve the strength through non-lanthanide alloy substitution, while preserving scintillation, have been demonstrated. Isovalent alloys having nominal compositions of comprising Al, Ga, Sc, Y, and In dopants as well as aliovalent alloys comprising Ca, Sr, Zr, Hf, Zn, and Pb dopants were prepared. All of these alloys exhibit bright fluorescence under UV excitation, with varying shifts in the spectral peaks and intensities relative to pure CeBr₃. Further, these alloys scintillate when coupled to a photomultiplier tube (PMT) and exposed to ¹³⁷Cs gamma rays.

Claims

1. A fracture-resistant, scintillation crystal, comprising a lanthanide-halide doped with one or more elements selected from the group or elements listed in Groups 2, 4, 12, 14 of the New IUPAC Periodic Table of the Elements, wherein the crystal exhibits a fracture toughness at least 50% greater than a fracture toughness of a corresponding undoped crystal.

2. The fracture-resistant, scintillation crystal of claim 1, wherein the dopant is a divalent cation.

3. The fracture-resistant, scintillation crystal of claim 2, wherein the dopant is selected from the list consisting of calcium, strontium, barium, zinc, cadmium, and lead.

4. The fracture-resistant, scintillation crystal of claim 1, wherein the dopant is a tetravalent cation.

5. The fracture-resistant, scintillation crystal of claim 4, wherein the dopant is zirconium or hafnium.

6. The fracture-resistant, scintillation crystal of claim 1, wherein the dopant is present in amounts of less than about 1500 ppm.

7. The fracture-resistant, scintillation crystal of claim 1, wherein the dopant is present in amounts of about 1000 ppm to about 500 ppm.

8. The scintillator crystal of claim 1, wherein the dopant is present in amounts of about 500 ppm to about 250 ppm.

9. The fracture-resistant, scintillation crystal of claim 1, wherein the lanthanide-halide is cerium (III) bromide.

10. The fracture-resistant, scintillation crystal of claim 9, wherein the average measured fracture toughness is equal to or greater than about 0.25 MPa√

{square root over (m)}.

11. A fracture-resistant, scintillation crystal, comprising cerium (III) bromide doped with a divalent or a tetravalent cation, wherein the cation is present in the crystal at a concentration of less than about 1500 ppm to greater than about 200 ppm, wherein the to scintillation crystal exhibits a fracture toughness of at least 50% greater than a fracture toughness of a corresponding undoped cerium (III) bromide crystal.

12. A method for preparing a fracture-resistant, scintillation crystal, comprising the steps of:

combining a quantity of a salt of an element selected form the list of elements is consisting of calcium, strontium, barium, zirconium, hafnium, zinc, cadmium, and lead, and a quantity of an lanthanide-halide to provide a combined material;

placing the combined material into an elongated crucible, wherein the crucible is chemically inert with respect to the element and the lanthanide-halide;

melting the combined material in a vacuum or under an inert atmosphere;

cooling the melted material to room temperature, wherein cooling takes place from one end and transitions to nucleate a single crystal at the one end, wherein the single crystal subsequently grows along the length of the elongated crucible as the melted material cools.

13. The method of claim 12, wherein the element is present in amounts of less than about 1500 ppm.

14. The method of claim 12, wherein the element is present in amounts of about 1000 ppm to about 500 ppm.

15. The method of claim 12, wherein the element is present in amounts of about 500 ppm to about 250 ppm.

16. The method of claim 12, wherein the lanthanide-halide is cerium (III) bromide.

17. The fracture-resistant, scintillation crystal of claim 16, wherein the average measured fracture toughness is equal to or greater than about 0.25 MPa√

{square root over (m)}.

18. A method for enhancing the fluorescence of a cerium (III) bromide crystal scintillator, comprising the step of introducing a quantity of a dopant element selected from the list of elements consisting of Ca, Sr, Ba, Sc, Y, Zr, Hf, Zn, Cd, Al, Ga, In, and Sn into the cerium (III) bromide crystal.