This disclosure relates to scintillator materials used for detecting ionizing radiation, such as X-rays, gamma rays and thermal neutron radiation, in security, medical imaging, particle physics and other applications. This disclosure relates particularly to chloride scintillator materials. Certain arrangements also relate to specific compositions of such scintillator material, method of making the same and devices with such scintillator materials as components.
Scintillator materials, which emit light pulses in response to impinging radiation, such as X-rays, gamma rays and thermal neutron radiation, are used in detectors that have a wide range of applications in medical imaging, particle physics, geological exploration, security and other related areas. Considerations in selecting scintillator materials typically include, but are not limited to, luminosity, decay time and emission wavelengths.
While a variety of scintillator materials have been made, there is a continuous need for superior scintillator materials.
The present disclosure relates generally to chloride scintillator materials and method of making such scintillator materials. In one arrangement, a chloride scintillator material is single-crystalline and has a composition of the formula A3MCl6, wherein A consists essentially of Li, Na K, Rb, Cs or any combination thereof, and M consists essentially of Ce, Sc, Y, La, Lu, Gd, Pr, Tb, Yb, Nd or any combination thereof. In another arrangement, a chloride scintillator material is single-crystalline and has a composition of the formula AM2Cl7, wherein A consists essentially of Li, Na K, Rb, Cs or any combination thereof, and M consists essentially of Ce, Sc, Y, La, Lu, Gd, Pr, Tb, Yb, Nd or any combination thereof. Specific examples of these scintillator materials include single-crystalline Cs3CeCl6, CsCe2Cl7, Ce-doped KGd2Cl7 (KGd2(1-x)Ce2xCl7) and Ce-doped CsGd2Cl7 (CsGd2(1-x)Ce2xCl7).
A further aspect of the present disclosure relates to a method of making chloride scintillator materials of the above-mentioned compositions. In one example, high-purity starting chlorides (such as CsCl and CeCl3) are mixed and melted to synthesize a compound of the desired composition of the scintillator material. A single crystal of the scintillator material is then grown from the synthesized compound by the Bridgman method, in which a sealed ampoule containing the synthesized compound is transported from a hot zone to a cold zone through a controlled temperature gradient at a controlled speed to form a single-crystalline scintillator from molten synthesized compound.
a) shows a scintillation decay time spectrum of a Cs3CeCl6 crystal; the spectrum was measured using 137Cs gamma-ray source (662 keV).
b) shows a scintillation decay time spectrum of a KGd2Cl7:Ce 1% (KGd2(1-x)Ce2xCl7, x=0.01) crystal; the spectrum was measured using 137Cs gamma-ray source (662 keV).
I. Overview
Inorganic scintillators are commonly used in nuclear and high-energy physics research, medical imaging, homeland security, and geological exploration. These materials typically possess sufficient stopping power for detection, high luminosity, high spectral energy resolution at room temperature and short decay time. Certain cerium-doped halides, such as LaCl3:Ce and LaBr3:Ce, have satisfactory scintillation properties at room temperature for gamma ray detection. Another desirable property of scintillators is a capability of neutron-gamma discrimination that is of importance for nuclear non-proliferation applications. Materials containing gadolinium, lithium and boron are employed to quickly and efficiently discriminate neutrons from gamma rays. Halide scintillators reported to date are produced mainly by the conventional Bridgman crystal growth method.
In one aspect of present disclosure, a chloride scintillator material is a single-crystalline material and has a composition of the formula A3MCl6, wherein A consists essentially of Li, Na, K, Rb, Cs or any combination thereof, and M consists essentially of Ce, Sc, Y, La, Lu, Gd, Pr, Tb, Yb, Nd or any combination thereof. In another aspect, a chloride scintillator material is a single-crystalline material and has a composition of the formula AM2Cl7, wherein A consists essentially of Li, Na K, Rb, Cs or any combination thereof, and M consists essentially of Ce, Sc, Y, La, Lu, Gd, Pr, Tb, Yb, Nd or any combination thereof. Specific examples of these scintillator materials include single-crystalline Cs3CeCl6, CsCe2Cl7, Ce-doped KGd2Cl7 (KGd2(1-x)Ce2xCl7) and Ce-doped CsGd2Cl7(CsGd2(1-x)Ce2xCl7).
Cs3CeCl6 and CsCe2Cl7 are congruently inciting compounds that exist in CsCl—CeCl3 system. This fact makes Cs3CeCl6 and CsCe2Cl7 suitable for practical crystal growth from a melt. Cs3CeCl6 has a density of 3.4 g/cm3, melts congruently at 804° C. and undergoes a solid-solid state transition at 401° C. Its high-temperature modification crystallizes in the cubic elpasolite type and a low-temperature modification in a monoclinic crystal structure. CsCe2Cl7 has a density of 3.6 g/cm3 and a hexagonal crystal structure KGd2Cl7 has an monoclinic crystal structure and melts congruently at 573° C. CsGd2Cl7 have a orthorhombic crystal structure and melts congruently at 680° C. Therefore they both can be grown from the melt.
In one aspect of the present disclosure, a method of growing a scintillator crystal described above includes synthesizing a compound of the composition discussed above and then growing a scintillator crystal from the synthesized compound. In one example, the synthesized compound is sealed in a quartz ampoule, which is pulled
In another aspect of the present disclosure, the above-described scintillator materials are used in radiation detection by scintillation. For example, a radiation detector can include a scintillator described above for generating photons in response to the impinging radiation. The scintillator is optically coupled to a photon detector, such as a photomultiplier tube (PMT), arranged to receive the photons generated by the scintillator and adapted to generate a signal indicative of the photon generation.
II. Example Configurations
(a) Scintillator Crystal Growth
In one arrangement, a modified 24-zone Electro-Dynamic Gradient Mellen furnace with a translation mechanism was used to grow Cs3CeCl6 and CsCe2Cl7 single crystals via the Bridgman technique. As a first step, these compounds were synthesized by mixing and melting starting anhydrous chlorides in quartz ampoules. Quartz ampoules were first baked and freshly cleaned by rinsing with a dilute HF solution and deionized water. High purity, anhydrous beads of starting compounds (e.g., CsCl and CeCl3 for Cs3CeCl6 and CsCe2Cl7; KCl and GdCl3 for KGd2Cl7 and CsCl and GdCl3 for CsGd2Cl7) (available from Sigma-Aldrich)) were loaded into the cylindrical quartz ampoules in a nitrogen-purged glove box and sealed under 10−6 mbar vacuum with a hydrogen torch. The relative amounts of the starting compounds in one arrangement were chosen to, achieve stoichiometry, of the synthesized scintillator material. Examples include 3 CsCl:1 CeCl3 for CS3CeCl6 and 1 CsCl:2 CeCl3 for CSCe2Cl7 (molecular ratios). Other ratios can be used for desired degree of stoichiometry.
The ampoule was heated up to, for example, 850° C., which is above the melting points of the starting chlorides. Then the synthesized compound was loaded into a specially designed quartz ampoule of about ½ in diameter to grow a single crystal, During the growth, the ampoule travels through the furnace from a hot zone (at a temperature which is above the inciting point of the composition) to a cold zone (at a temperature which is below the inciting point of the composition) at a rate of ˜1-2 mm/h. Cooling down was done at a rate of about 10° C./h. After the crystals were grown and removed from the growth ampoules, they were stored in mineral oil to protect from the atmosphere.
(b) Characterization of Scintillator Crystals
Certain samples were characterized without polishing while for certain others, plates of about 1-2 mm thickness were cut from the boules and polished using a set of sand papers and mineral oil. To identify the obtained phase, powder X-ray diffraction (XRD) analysis was carried out in air at room temperature. To minimize the effects of self-absorption, small samples (typically 1-2 mm thick, 3 mm×3 mm) were selected for the optical characterization.
Photoluminescence spectra were obtained with a Horiba Jobin Yvon Fluorolog3 spectrofluorometer equipped with Xe lamp and monochromators. Scintillation time profiles were recorded using the time-correlated single photon technique and a 137Cs gamma-ray source. Radioluminescence spectra were measured at—room temperature under continuous irradiation, from an X-ray generator (35 kV and 0.1 mA). Light output measurements were carried out on samples covered in mineral oil and directly coupled to a photomultiplier tube (PMT) and covered with Teflon tape. A Hamamatsu 3177-50 PMT was used for absolute light output measurements. Gamma-ray energy spectra were recorded using a 137Cs source with a 2 ms shaping time. The integral quantum efficiency of the PMT according to the emission spectrum of the scintillators was used to calculate the number of photons per unit gamma ray energy. The energy resolution, at 662 keV was determined from the full-width at half-maximum (FWHM) of the 662 keV photopeak.
(c) Example Results
According to certain aspects of the present disclosure, single crystals of the chloride materials suitable for scintillator applications were made, and their scintillation properties were measured. A single crystal of Cs3CeCl6 made using the Bridgman method as described above is shown in the image in
The above samples were confirmed to be single phase by X-ray diffraction analysis. As an example,
The single crystal scintillators described above have demonstrated high performance under optical, X-ray, gamma ray, and thermal neutron excitations. These scintillators exhibit Ce 5d-4-f luminescence.
Measurements on additional, polished samples were performed.
In addition to X-ray detection, certain single crystals with a combination of Gd and Ce according to an aspect of the present disclosure can be effective in thermal neutron detection due to the large cross-section for thermal neutron absorption for Gd isotopes, in particular 157Gd and 155Gd. For example, effective thermal neutron detection was observed for KGd2Cl7 and CsGd2Cl7.
III. Summary
Thus, chloride scintillator crystals with excellent scintillation properties have been produced according to the present disclosure. Because many embodiments of the invention can be made without departing from the spirit and scope of the invention, the invention resides in the claims hereinafter appended.
The present application claims the benefit of U.S. Provisional Application Ser. No. 61/332,972, filed May 10, 2010. The present application also relates to commonly assigned non-provisional U.S. patent application entitled “IODIDE SCINTILLATOR FOR RADIATION DETECTION”, filed on the same day as the present application and claiming the benefit of U.S. Provisional Application Ser. No. 61/332,945, filed May 10, 2010 and non-provisional U.S. patent application entitled “HALIDE SCINTILLATOR FOR RADIATION DETECTION”, filed on the same day as the present application and claiming the benefit of U.S. Provisional Application Ser. No. 61/332,934, filed May 10, 2010. All applications are incorporated herein by reference.
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