WO2015017384A2 - Lanthanum-yttrium oxide scintillators and use thereof - Google Patents
Lanthanum-yttrium oxide scintillators and use thereof Download PDFInfo
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- WO2015017384A2 WO2015017384A2 PCT/US2014/048566 US2014048566W WO2015017384A2 WO 2015017384 A2 WO2015017384 A2 WO 2015017384A2 US 2014048566 W US2014048566 W US 2014048566W WO 2015017384 A2 WO2015017384 A2 WO 2015017384A2
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01T—MEASUREMENT OF NUCLEAR OR X-RADIATION
- G01T1/00—Measuring X-radiation, gamma radiation, corpuscular radiation, or cosmic radiation
- G01T1/16—Measuring radiation intensity
- G01T1/20—Measuring radiation intensity with scintillation detectors
- G01T1/202—Measuring radiation intensity with scintillation detectors the detector being a crystal
- G01T1/2023—Selection of materials
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K11/00—Luminescent materials, e.g. electroluminescent or chemiluminescent
- C09K11/08—Luminescent materials, e.g. electroluminescent or chemiluminescent containing inorganic luminescent materials
- C09K11/77—Luminescent materials, e.g. electroluminescent or chemiluminescent containing inorganic luminescent materials containing rare earth metals
- C09K11/7783—Luminescent materials, e.g. electroluminescent or chemiluminescent containing inorganic luminescent materials containing rare earth metals containing two or more rare earth metals one of which being europium
- C09K11/7784—Chalcogenides
- C09K11/7787—Oxides
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01T—MEASUREMENT OF NUCLEAR OR X-RADIATION
- G01T1/00—Measuring X-radiation, gamma radiation, corpuscular radiation, or cosmic radiation
- G01T1/16—Measuring radiation intensity
- G01T1/20—Measuring radiation intensity with scintillation detectors
- G01T1/202—Measuring radiation intensity with scintillation detectors the detector being a crystal
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- G—PHYSICS
- G21—NUCLEAR PHYSICS; NUCLEAR ENGINEERING
- G21K—HANDLING OF PARTICLES OR IONISING RADIATION NOT OTHERWISE PROVIDED FOR; IRRADIATION DEVICES; GAMMA RAY OR X-RAY MICROSCOPES
- G21K4/00—Conversion screens for the conversion of the spatial distribution of X-rays or particle radiation into visible images, e.g. fluoroscopic screens
Definitions
- the disclosure relates to lanthanum-yttrium oxide scintillators used for detecting radiation, such as X-rays, gamma rays and thermal neutron radiation and charged particles, in security, medical imaging, particle physics and other applications.
- Figure 1 depicts samples (left) and transmission electron microscopy (TEM) images of Lao. 2 Y 1 .8O3 (right).
- the size of the two samples on the left is about 1 cm and the particle size in the TEM image is about 50 nm.
- Figure 2 depicts the X-ray excited luminescence of Lao. 2 Y 1 .sO 3 .
- Figure 3 depicts the X-ray diffraction (XRD) of Lao. 2 Y 1 .sO 3 .
- Figure 4 depicts the X-ray photoelectron spectroscopy (XPS) of Lao. 2 Y 1 .sO 3 .
- Figure 5 depicts the absorption spectrum of Lao. 2 Y 1 .sO 3 .
- Figure 6 depicts the X-ray excited emission spectra of Lao. 2 Y 1 .sO 3 and 2% 2,5- diphenyloxazole in polyvinyl toluene.
- Figures 7A and 7B depict the energy calibration curve for 1 ⁇ Ba 133 source with energy resolution of 4.97% (Figure 7A) and for 1 ⁇ Na-22 with energy resolution of 4.55% (Figure 7B). Total number of counts is 12 cps ( Figure 7A) and 15 cps ( Figure 7B).
- Figures 8A-8F depict the energy spectra of Lao. 2 Y 1 .sO 3 tested with Cs-137 (Figure 8A) and Co-60 ( Figure 8B), Nal tested with Cs-137 (Figure 8C) and Co-60 ( Figure 8D), and Csl tested with Cs-137 (Figure 8E) and Co-60 ( Figure 8F).
- Figure 9 depicts the luminescence decay curve of a Lao.2Y1.sO 3 glass sample.
- Figure 10A is the X-ray excited luminescence of Lao.05Y1.95O3 and Figure 10B is the U.V. photo luminescence of Lao.05Y1.95O3.
- Figure 11A is the X-ray excited luminescence of Lao.3Y1.7O3 and Figure 11B is the photoluminescence of Lao.3Y1.7O3.
- Ranges may be expressed herein as from “about” one particular value, and/or to "about” another particular value. When such a range is expressed, another aspect includes from the one particular value and/or to the other particular value. Similarly, when values are expressed as approximations, by use of the antecedent "about,” it will be understood that the particular value forms another aspect. It will be further understood that the endpoints of each of the ranges are significant both in relation to the other endpoint, and independently of the other endpoint.
- Values expressed as “greater than” do not include the lower value.
- the "variable x" is defined as “greater than zero” expressed as "0 ⁇ x” the value of x is any value, fractional or otherwise that is greater than zero.
- values expressed as “less than” do not include the upper value.
- the "variable x" is defined as “less than 2" expressed as “x ⁇ 2" the value of x is any value, fractional or otherwise that is less than 2.
- any embodiment of any of the apparatuses, systems, and methods can consist of or consist essentially of - rather than comprise/include/contain/have - any of the described steps, elements, and/or features.
- the term “consisting of or “consisting essentially of” can be substituted for any of the open-ended linking verbs recited above, in order to change the scope of a given claim from what it would otherwise be using the open- ended linking verb.
- the disclosed methods utilize luminescent metal oxide scintillators comprising metals chosen from lanthanum (La), lutetium (Lu), scandium (Sc) or yttrium (Y), the disclosed scintillators having the Formula (I):
- A is an element chosen from La, Y, Lu or Sc;
- B is an element chosen from La, Y, Lu or Sc;
- a and B are not the same element
- the index x is greater than 0 and less than 2 (0 ⁇ x ⁇ 2).
- the scintillators when prepared can have a particle size of from about 0.1 nm to about
- the disclosed scintillators are formed into a glass having a thickness and configuration determined by the formulator.
- the resulting glass can be adapted for use in the methods and devices described herein.
- the disclosed scintillators have the formula La x Y 2 _ x 0 3 wherein the value of x is 0 ⁇ x ⁇ 2.
- Non-limiting examples of this aspect include: La 0 .iYi.9O 3 ; La 0 . 2 Yi.8O 3 ;
- the disclosed scintillators have the formula Lu x Y 2 _ x 0 3 wherein the value of x is 0 ⁇ x ⁇ 2.
- Non-limiting examples of this aspect include: Lu 0 .iYi.9O 3 ; Lu 0 . 2 Yi.8O 3 ;
- the disclosed scintillators have the formula Sc x Y 2 _ x 0 3 wherein the value of x is 0 ⁇ x ⁇ 2.
- Non-limiting examples of the aspect include: Sco.iYi. 0 3 ; Sco. 2 Yi.s0 3 ;
- the index x is from 0.5 to 0.8. In another aspect the index x is from 0.01 to 0.1. As such, the value of the index x for the disclosed scintillators can, for example, 0.01 , 0.01 1 , 0.012, 0.013, 0.014, 0.015, 0.016, 0.017, 0.018,
- the disclosed scintillators display luminescence in blue-green region of visible light when excited with X-rays and exhibit a comparable energy resolution to that exhibited by Nal and Csl scintillators.
- scintillators having the formula La x Y 2 _ x 0 3 are stable and have luminescence decay lifetimes of approximately 300 ps. As such, the use of the disclosed scintillators provides a means for detection of radiation.
- the disclosed scintillators upon excitation emit electromagnetic radiation.
- photoluminescence refers to electromagnetic radiation emitted when UV light is used as a source of excitation.
- X-ray induced optical luminescence and X-ray fluorescence is emission under X-ray excitation.
- the scintillators when prepared can have a particle size of from about 0.1 nm to about 500 nm.
- the disclosed scintillators are formed into a glass having a thickness and configuration determined by the formulator. The resulting glass can be adapted for use in the methods and devices described herein.
- EXAMPLE 1 The disclosed La x Y 2 _ x 0 3 nanomaterials are synthesized using a solid state reaction. First, yttrium oxide (Y 2 0 3 ) powder and lanthanum nitrate hydrate (La(N0 3 ) 3 6H 2 0) are admixed and stirred in ethanol for 24 hours. The amount of Y 2 0 3 and La(N0 3 ) 3 ' 6H 2 0 which is used is dependent upon the desired stoichiometry of the final scintillator, i.e., the value of "x" in the general formula, La x Y 2 - x 0 3 . After stirring is complete, the mixture is then dried and calcined at 1100 °C for 10 hours to obtain the desired scintillator in the form of nanocrystals.
- Y 2 0 3 yttrium oxide
- La(N0 3 ) 3 6H 2 0 lanthanum nitrate
- the formation of the disclosed scintillators into a glass can be accomplished as follows.
- the nanomaterial prepared above is charged to a crucible and calcined at 1500 °C for 2 hours.
- the resulting melt is poured into a mold and slowly cooled to room temperature.
- the resulting glass can be cut into any shape desired by the formulator.
- a disclosed scintillator as a glass La 0 . 2 Yi. 8 O 3 , is used to demonstrate the scintillation luminescence depicted below.
- Figure 2 depicts the X-ray induced luminescence of an example of the disclosed scintillators having the formula La x Y 2 _ x 0 3 .
- the emission spectrum of Lao. 2 Yi. 8 0 3 is centered at approximately 460 nm with an intensity of approximately 580 counts per second. Without wishing to be limited by theory, these emissions are believed to result from defects or electron-hole pairs or donor-acceptor pairs in the crystals.
- the disclosed scintillators can be used for radiation detection, including alpha radiation, beta radiation, gamma radiation, neutron radiation, cosmic rays, and the like.
- the disclosed scintillators can be used for medical imaging, for example, X-ray intensification, detectors for computed tomography (CT), position-emission tomography (PET) and computed radiography (CR). Further, the disclosed scintillators can be used for cathodoluminescence induced by electron beams for monitor screens, including televisions, computers, and any displays related to cathodoluminescence or electron beams.
- CT computed tomography
- PET position-emission tomography
- CR computed radiography
- the disclosed scintillators can be used for cathodoluminescence induced by electron beams for monitor screens, including televisions, computers, and any displays related to cathodoluminescence or electron beams.
- the formation of the disclosed scintillators into a glass can be accomplished as follows.
- the nanomaterial prepared above is charged to a crucible and calcined at 1500 °C for 2 hours.
- the resulting melt is poured into a mold and slowly cooled to room temperature.
- the resulting glass can be cut into any shape desired by the formulator.
- a disclosed scintillator as a glass Lao.2Y1.sO3
- TABLE I provides the energy resolution and detection efficiency of an example of a disclosed scintillator, Lao.2Y1.sO3 when exposed to various sources of
- Figure 1 depicts glass samples prepared at 1100 °C using nanoparticle powders comprising Lao.2Y1.sO3 and the TEM images of the sample.
- This glass sample was prepared using nanoparticle having an average size of approximately 50 nm. Both the nanoparticle powder and the glass samples were shown to have intense X-ray excited luminescence.
- FIG. 2 shows the X-ray diffraction (XRD) pattern of a disclosed scintillator, Lao.2Y1.sO3, that has been formed into a glass.
- Figure 4 shows X-ray photoelectron spectrum (XPS) of the same sample.
- the XRD pattern indicates that the material is well crystallized and the peaks correspond to the cubic Y2O3 phase, with no additional phases present. This means that La 2 0 3 is completely dissolved in Y2O3 when heated at temperatures higher than 1100° C.
- the XPS confirms the presence of La, Y and O.
- Lao.2Y1.8O3 glass sample shows an absorption edge at around 240 nm and a peak at 213 nm.
- the X-ray excited luminescence of Lao.2Y1.sO3 glass is more than 110 times that of PVT/PPO (2% PPO) of about the same dimension. All these characteristics indicate that Lao.2Y1.8O3 is a good scintillator for radiation detection.
- Lao. 2 Y 1 . 8 O 3 , Nal, and Csl tested with Cs-137 and Co-60 ( Figures 8A-8F), the values are as follows.
- the Lao. 2 Y 1 .sO 3 sample tested had a volume of 0.07 cm 3 .
- the energy resolution for 5 ⁇ Cs-137 was 4.30% and the total number of counts is 37 cps ( Figure 8A).
- the photo peaks for 1 ⁇ Co-60 are not seen clearly, but bumps around 1.13 MeV and 1.36 MeV are detected ( Figure 8B). Total number of counts is 50 cps.
- the Nal sample tested had a volume of 16.4 cm 3 .
- the energy resolution of the 0.662 MeV peak with Cs-137 is 4.14% and total counts is 12125 cps (Figure 8C).
- the energy resolution of the 1.17 MeV peak with Co-60 is 8.1%> and that of the 1.33 MeV is 4.02% ( Figure 8D).
- Total number of counts is 14936 cps.
- the Csl sample tested had a volume of 1 cm 3 .
- the energy resolution with Cs-137 was 4.57%> and total number of counts was 227 cps (Figure 8E).
- the total number of counts with Co-60 was 21 cps ( Figure 8F).
- Lao. 2 Y 1 .sO 3 has an energy resolution comparable to that of Csl and Nal scintillators.
- TABLE II provides the energy resolution and detection efficiency of an example of a disclosed scintillator, Lao. 2 Y 1 .sO 3 when exposed to various sources of radioactivity.
- the disclosure relates to lanthanum-yttrium oxide scintillators used for detecting radiation, such as X-rays, gamma rays, beta-rays, protons, electrons, and thermal neutron radiation and charged particles.
- the scintillators can be used for in security, medical imaging, particle physics, space, soil, and other applications.
- a method for detecting the presence of a radioactive element or a source of radiation comprising:
- A is chosen from La, Y, Lu or Sc;
- B is chosen from La, Y, Lu or Sc;
- a and B are not the same element; the index x is greater than 0 and less than 2 (0 ⁇ x ⁇ 2);
- the impinging radiation causes the scintillator to emit electromagnetic radiation
- a radioactive element or a source of radiation comprising:
- A is chosen from La, Y, Lu or Sc;
- B is chosen from La, Y, Lu or Sc;
- a and B are not the same element
- the index x is greater than 0 and less than 2 (0 ⁇ x ⁇ 2);
- a method for detecting the presence of a radioactive element or a source of radiation comprising:
- A is chosen from La, Y, Lu or Sc;
- B is chosen from La, Y, Lu or Sc;
- a and B are not the same element
- the index x is greater than 0 and less than 2 (0 ⁇ x ⁇ 2);
- impinging radiation causes the X-ray induced luminescence or fluorescence
- measuring is meant either quantifying, qualifying the photoluminescence or providing both types of measurements.
- the wavelength of the emitted electromagnetic radiation can be used to qualify the source of radiation, for example, to correlate the wavelength of the emission with a particular source of radiation.
- the intensity of the emission can be used to quantify the amount of radiation being received.
- the formulator can therefore utilize the disclosed scintillators to identify the source of the radiation, for example, the element or elements producing the radiation, as well as the relative amounts of each.
- impinge means to contact, strike, hit, collide with or otherwise make contact.
- radiation impinges the scintillator when the radiation makes contact with the scintillator.
- electromagnetic radiation as meant herein is used in the accepted scientific definition.
- An example of electromagnetic radiation includes visible light which is one resultant of photo luminescence.
- a method for detecting the presence of a source of radiation comprising:
- scintillator comprising Lao.2Y1.sO3, wherein the impinging X-rays cause the scintillator to emit X-ray induced optical luminescence or X-ray fluorescence;
- the photoluminescence can be measured, quantified or qualified by any means chosen by the formulator. See Resch-Genger et al., "Characterization of photoluminescence measuring systems (IUPAC Technical Report),” Pure Appl. Chem., Vol. 84, No. 8, pp. 1815- 1835, (2012) for a discussion of photoluminescence detection.
- a scintillator having the formula:
- B is chosen from La, Y, Lu or Sc;
- a and B are not the same element
- the index x is greater than 0 and less than 2 (0 ⁇ x ⁇ 2);
- the scintillator is fabricated into a thin transparent or translucent glass onto which radiation impinges.
- the glass is configured with a detector which detects any electromagnetic radiation that is emitted by the scintillator and which is used to verify the presence of a radiation source.
- the electromagnetic radiation emitted by the scintillator can be photo luminescence, X-ray induced optical luminescence or X-ray fluorescence.
- Also disclosed herein is the use of the disclosed scintillators for detecting the presence of suspected radiation. For example, within a security setting, a person trying to transport a source of radiation can be detected using the disclosed scintillators. In addition, cargo containers, packages, and the like can be examined for a hidden source of radiation.
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Abstract
The disclosure relates to lanthanum-yttrium oxide scintillators used for detecting radiation, such as X-rays, gamma rays and thermal neutron radiation and charged particles, security, medical imaging, particle physics and other applications.
Description
LANTHANUM-YTTRIUM OXIDE SCINTILLATORS
AND USE THEREOF
CROSS REFERENCE TO RELATED APPLICATIONS
This application claims the benefit of Provisional Application Serial Number
61/859,466, filed on July 29, 2013, the entire disclosure of which is incorporated herein by reference in its entirety.
FIELD
The disclosure relates to lanthanum-yttrium oxide scintillators used for detecting radiation, such as X-rays, gamma rays and thermal neutron radiation and charged particles, in security, medical imaging, particle physics and other applications.
BRIEF DESCRIPTION OF THE DRAWINGS
The following drawings illustrate by way of example and not limitation. For the sake of brevity and clarity, every feature of a given structure is not always labeled in every figure in which that structure appears.
Figure 1 depicts samples (left) and transmission electron microscopy (TEM) images of Lao.2Y1.8O3 (right). The size of the two samples on the left is about 1 cm and the particle size in the TEM image is about 50 nm.
Figure 2 depicts the X-ray excited luminescence of Lao.2Y1.sO3.
Figure 3 depicts the X-ray diffraction (XRD) of Lao.2Y1.sO3.
Figure 4 depicts the X-ray photoelectron spectroscopy (XPS) of Lao.2Y1.sO3.
Figure 5 depicts the absorption spectrum of Lao.2Y1.sO3.
Figure 6 depicts the X-ray excited emission spectra of Lao.2Y1.sO3 and 2% 2,5- diphenyloxazole in polyvinyl toluene.
Figures 7A and 7B depict the energy calibration curve for 1 μθ Ba 133 source with energy resolution of 4.97% (Figure 7A) and for 1 μθ Na-22 with energy resolution of 4.55% (Figure 7B). Total number of counts is 12 cps (Figure 7A) and 15 cps (Figure 7B).
Figures 8A-8F depict the energy spectra of Lao.2Y1.sO3 tested with Cs-137 (Figure 8A) and Co-60 (Figure 8B), Nal tested with Cs-137 (Figure 8C) and Co-60 (Figure 8D), and Csl tested with Cs-137 (Figure 8E) and Co-60 (Figure 8F).
Figure 9 depicts the luminescence decay curve of a Lao.2Y1.sO3 glass sample.
Figure 10A is the X-ray excited luminescence of Lao.05Y1.95O3 and Figure 10B is the U.V. photo luminescence of Lao.05Y1.95O3.
Figure 11A is the X-ray excited luminescence of Lao.3Y1.7O3 and Figure 11B is the photoluminescence of Lao.3Y1.7O3.
DETAILED DESCRIPTION
The materials, scintillators, compositions, articles, and methods described herein may be understood more readily by reference to the following detailed description of specific aspects of the disclosed subject matter and the Examples included therein.
Before the present materials, scintillators, compositions, and methods are disclosed and described, it is to be understood that the aspects described below are not limited to specific synthetic methods or specific reagents, as such may, of course, vary. It is also to be understood that the terminology used herein is for the purpose of describing particular aspects only and is not intended to be limiting.
Also, throughout this specification, various publications are referenced. The disclosures of these publications in their entireties are hereby incorporated by reference into this application in order to more fully describe the state of the art to which the disclosed matter pertains. The references disclosed are also individually and specifically incorporated by reference herein for the material contained in them that is discussed in the sentence in which the reference is relied upon.
General Definitions
In this specification and in the claims that follow, reference will be made to a number of terms, which shall be defined to have the following meanings:
All percentages, ratios and proportions herein are by weight, unless otherwise specified.
All temperatures are in degrees Celsius (° C) unless otherwise specified.
The terms "a" and "an" are defined as one or more unless this disclosure explicitly requires otherwise.
Ranges may be expressed herein as from "about" one particular value, and/or to "about" another particular value. When such a range is expressed, another aspect includes from the one particular value and/or to the other particular value. Similarly, when values are expressed as approximations, by use of the antecedent "about," it will be understood that the particular value
forms another aspect. It will be further understood that the endpoints of each of the ranges are significant both in relation to the other endpoint, and independently of the other endpoint.
Values expressed as "greater than" do not include the lower value. For example, when the "variable x" is defined as "greater than zero" expressed as "0 < x" the value of x is any value, fractional or otherwise that is greater than zero.
Similarly, values expressed as "less than" do not include the upper value. For example, when the "variable x" is defined as "less than 2" expressed as "x < 2" the value of x is any value, fractional or otherwise that is less than 2.
"Optional" or "optionally" means that the subsequently described event or circumstance can or cannot occur, and that the description includes instances where the event or
circumstance occurs and instances where it does not.
The terms "comprise" (and any form of comprise, such as "comprises" and
"comprising"), "have" (and any form of have, such as "has" and "having"), "include" (and any form of include, such as "includes" and "including") and "contain" (and any form of contain, such as "contains" and "containing") are open-ended linking verbs. As a result, an apparatus that "comprises," "has," "includes" or "contains" one or more elements possesses those one or more elements, but is not limited to possessing only those elements. Likewise, a method that "comprises," "has," "includes" or "contains" one or more steps possesses those one or more steps, but is not limited to possessing only those one or more steps.
Any embodiment of any of the apparatuses, systems, and methods can consist of or consist essentially of - rather than comprise/include/contain/have - any of the described steps, elements, and/or features. Thus, in any of the claims, the term "consisting of or "consisting essentially of can be substituted for any of the open-ended linking verbs recited above, in order to change the scope of a given claim from what it would otherwise be using the open- ended linking verb.
The feature or features of one embodiment may be applied to other embodiments, even though not described or illustrated, unless expressly prohibited by this disclosure or the nature of the embodiments.
1. SCINTILLATORS
The disclosed methods utilize luminescent metal oxide scintillators comprising metals chosen from lanthanum (La), lutetium (Lu), scandium (Sc) or yttrium (Y), the disclosed scintillators having the Formula (I):
AxB2_x03
(I)
wherein A is an element chosen from La, Y, Lu or Sc;
B is an element chosen from La, Y, Lu or Sc;
provided that A and B are not the same element;
the index x is greater than 0 and less than 2 (0 < x < 2).
The scintillators when prepared can have a particle size of from about 0.1 nm to about
500 nm. In one embodiment the disclosed scintillators are formed into a glass having a thickness and configuration determined by the formulator. The resulting glass can be adapted for use in the methods and devices described herein.
In one aspect the disclosed scintillators have the formula LaxY2_x03 wherein the value of x is 0 < x < 2. Non-limiting examples of this aspect include: La0.iYi.9O3; La0.2Yi.8O3;
La0.3Yi.7O3; La0.4Yi.6O3; La0.5Yi.5O3; and La0.6Yi.4O3.
In a further aspect the disclosed scintillators have the formula LuxY2_x03 wherein the value of x is 0 < x < 2. Non-limiting examples of this aspect include: Lu0.iYi.9O3; Lu0.2Yi.8O3;
Lu0.3Yi.7O3; Lu0.4Yi.6O3; Lu0.5Yi.5O3; and Lu0.6Yi.4O3.
In another aspect the disclosed scintillators have the formula ScxY2_x03 wherein the value of x is 0 < x < 2. Non-limiting examples of the aspect include: Sco.iYi. 03; Sco.2Yi.s03;
Sc0.3Yi.7O3; Sco.4Yi.e03; Sco.5Y1.5O5; and Sco.eYi.403.
In one aspect of the disclosed scintillators the index x is from 0.5 to 0.8. In another aspect the index x is from 0.01 to 0.1. As such, the value of the index x for the disclosed scintillators can, for example, 0.01 , 0.01 1 , 0.012, 0.013, 0.014, 0.015, 0.016, 0.017, 0.018,
0.019, 0.02, 0.021 , 0.022, 0.023, 0.024, 0.025, 0.026, 0.027, 0.028, 0.029, 0.03, 0.031 , 0.032,
0.033, 0.034, 0.035, 0.036, 0.037, 0.038, 0.039, 0.04, 0.041 , 0.042, 0.043, 0.044, 0.045, 0.046,
0.047, 0.048, 0.049, 0.05, 0.051 , 0.052, 0.053, 0.054, 0.055, 0.056, 0.057, 0.058, 0.059, 0.06,
0.061 , 0.062, 0.063, 0.064, 0.065, 0.066, 0.067, 0.068, 0.069, 0.07, 0.071 , 0.072, 0.073, 0.074, 0.075, 0.076, 0.077, 0.078, 0.079, 0.08, 0.081 , 0.082, 0.083, 0.084, 0.085, 0.086, 0.087, 0.088,
0.089, 0.09, 0.091 , 0.092, 0.093, 0.094, 0.095, 0.096, 0.097, 0.098, 0.099, 0.1 , 0.1 1 , 0.12, 0.13,
0.14, 0.15, 0.16, 0.17, 0.18, 0.19, 0.2, 0.21, 0.22, 0.23, 0.24, 0.25, 0.26, 0.27, 0.28, 0.29, 0.3, 0.31, 0.32, 0.33, 0.34, 0.35, 0.36, 0.37, 0.38, 0.39, 0.4, 0.41, 0.42, 0.43, 0.44, 0.45, 0.46, 0.47, 0.48, 0.49, 0.5, 0.51, 0.52, 0.53, 0.54, 0.55, 0.56, 0.57, 0.58, 0.59, 0.6, 0.61, 0.62, 0.63, 0.64, 0.65, 0.66, 0.67, 0.68, 0.69, 0.7, 0.71, 0.72, 0.73, 0.74, 0.75, 0.76, 0.77, 0.78, 0.79, 0.8, 0.81, 0.82, 0.83, 0.84, 0.85, 0.86, 0.87, 0.88, 0.89, 0.9, 0.91, 0.92, 0.93, 0.94, 0.95, 0.96, 0.97, 0.98, 0.99, 1.01, 1.011, 1.012, 1.013, 1.014, 1.015, 1.016, 1.017, 1.018, 1.019, 1.02, 1.021, 1.022, 1.023, 1.024, 1.025, 1.026, 1.027, 1.028, 1.029, 1.03, 1.031, 1.032, 1.033, 1.034, 1.035, 1.036, 1.037, 1.038, 1.039, 1.04, 1.041, 1.042, 1.043, 1.044, 1.045, 1.046, 1.047, 1.048, 1.049, 1.05, 1.051, 1.052, 1.053, 1.054, 1.055, 1.056, 1.057, 1.058, 1.059, 1.06, 1.061, 1.062, 1.063, 1.064, 1.065, 1.066, 1.067, 1.068, 1.069, 1.07, 1.071, 1.072, 1.073, 1.074, 1.075, 1.076, 1.077, 1.078, 1.079, 1.08, 1.081, 1.082, 1.083, 1.084, 1.085, 1.086, 1.087, 1.088, 1.089, 1.09, 1.091, 1.092, 1.093, 1.094, 1.095, 1.096, 1.097, 1.098, 1.099, 1.1, 1.11, 1.12, 1.13, 1.14, 1.15, 1.16, 1.17, 1.18, 1.19, 1.2, 1.21, 1.22, 1.23, 1.24, 1.25, 1.26, 1.27, 1.28, 1.29, 1.3, 1.31, 1.32, 1.33, 1.34, 1.35, 1.36, 1.37, 1.38, 1.39, 1.4, 1.41, 1.42, 1.43, 1.44, 1.45, 1.46, 1.47, 1.48, 1.49, 1.5, 1.51, 1.52, 1.53, 1.54, 1.55, 1.56, 1.57, 1.58, 1.59, 1.6, 1.61, 1.62, 1.63, 1.64, 1.65, 1.66, 1.67, 1.68, 1.69, 1.7, 1.71, 1.72, 1.73, 1.74, 1.75, 1.76, 1.77, 1.78, 1.79, 1.8, 1.81, 1.82, 1.83, 1.84, 1.85, 1.86, 1.87, 1.88, 1.89, 1.9, 1.91, 1.92, 1.93, 1.94, 1.95, 1.96, 1.97, 1.98 and 1.99.
The disclosed scintillators display luminescence in blue-green region of visible light when excited with X-rays and exhibit a comparable energy resolution to that exhibited by Nal and Csl scintillators. For example, scintillators having the formula LaxY2_x03 are stable and have luminescence decay lifetimes of approximately 300 ps. As such, the use of the disclosed scintillators provides a means for detection of radiation.
The disclosed scintillators upon excitation emit electromagnetic radiation. The term "photoluminescence" refers to electromagnetic radiation emitted when UV light is used as a source of excitation. X-ray induced optical luminescence and X-ray fluorescence is emission under X-ray excitation.
The scintillators when prepared can have a particle size of from about 0.1 nm to about 500 nm. In one embodiment the disclosed scintillators are formed into a glass having a thickness and configuration determined by the formulator. The resulting glass can be adapted for use in the methods and devices described herein.
EXAMPLE 1
The disclosed LaxY2_x03 nanomaterials are synthesized using a solid state reaction. First, yttrium oxide (Y203) powder and lanthanum nitrate hydrate (La(N03)36H20) are admixed and stirred in ethanol for 24 hours. The amount of Y203 and La(N03)3 '6H20 which is used is dependent upon the desired stoichiometry of the final scintillator, i.e., the value of "x" in the general formula, LaxY2-x03. After stirring is complete, the mixture is then dried and calcined at 1100 °C for 10 hours to obtain the desired scintillator in the form of nanocrystals.
The formation of the disclosed scintillators into a glass can be accomplished as follows. The nanomaterial prepared above is charged to a crucible and calcined at 1500 °C for 2 hours. The resulting melt is poured into a mold and slowly cooled to room temperature. The resulting glass can be cut into any shape desired by the formulator. One example of a disclosed scintillator as a glass, La0.2Yi.8O3, is used to demonstrate the scintillation luminescence depicted below.
TABLE I provides examples of the disclosed scintillators and their photoluminescence and X-ray induced emission.
TABLE I
Figure 2 depicts the X-ray induced luminescence of an example of the disclosed scintillators having the formula LaxY2_x03. As seen in Figure 2 the emission spectrum of Lao.2Yi.803 is centered at approximately 460 nm with an intensity of approximately 580 counts per second. Without wishing to be limited by theory, these emissions are believed to result from defects or electron-hole pairs or donor-acceptor pairs in the crystals. As such, the disclosed scintillators can be used for radiation detection, including alpha radiation, beta radiation, gamma radiation, neutron radiation, cosmic rays, and the like. In addition, the disclosed scintillators can be used for medical imaging, for example, X-ray intensification, detectors for computed tomography (CT), position-emission tomography (PET) and computed radiography (CR). Further, the disclosed scintillators can be used for cathodoluminescence
induced by electron beams for monitor screens, including televisions, computers, and any displays related to cathodoluminescence or electron beams.
The formation of the disclosed scintillators into a glass can be accomplished as follows. The nanomaterial prepared above is charged to a crucible and calcined at 1500 °C for 2 hours. The resulting melt is poured into a mold and slowly cooled to room temperature. The resulting glass can be cut into any shape desired by the formulator. One example of a disclosed scintillator as a glass, Lao.2Y1.sO3, is used to demonstrate the scintillation luminescence depicted below. TABLE I provides the energy resolution and detection efficiency of an example of a disclosed scintillator, Lao.2Y1.sO3 when exposed to various sources of
radioactivity.
Figure 1 depicts glass samples prepared at 1100 °C using nanoparticle powders comprising Lao.2Y1.sO3 and the TEM images of the sample. This glass sample was prepared using nanoparticle having an average size of approximately 50 nm. Both the nanoparticle powder and the glass samples were shown to have intense X-ray excited luminescence.
As depicted in Figure 2, when the disclosed scintillators are prepared in the form of a glass and subjected to gamma radiation, photopeaks are detected. Figure 3 shows the X-ray diffraction (XRD) pattern of a disclosed scintillator, Lao.2Y1.sO3, that has been formed into a glass. Figure 4 shows X-ray photoelectron spectrum (XPS) of the same sample. The XRD pattern indicates that the material is well crystallized and the peaks correspond to the cubic Y2O3 phase, with no additional phases present. This means that La203 is completely dissolved in Y2O3 when heated at temperatures higher than 1100° C. The XPS confirms the presence of La, Y and O.
This sample is transparent and its absorption spectrum is shown in Figure 5. The Lao.2Y1.8O3 glass sample shows an absorption edge at around 240 nm and a peak at 213 nm. As shown in Figure 6, the X-ray excited luminescence of Lao.2Y1.sO3 glass is more than 110 times that of PVT/PPO (2% PPO) of about the same dimension. All these characteristics indicate that Lao.2Y1.8O3 is a good scintillator for radiation detection.
Tables 1 and 2 below, as well as the spectra shown Figure 7A and Figure 7B
demonstrate that this example of a disclosed scintillator, Lao.2Y1.sO3, demonstrates scintillation properties, particularly for low energy isotopes like Ba-133 and Na-22. For Cs-137, Ba-133 and Ba-22, Lao.2Y1.sO3 sharp photopeaks are observed. The energy resolution and detector
efficiency were calculated and shown the legends for Figure 7 A and Figure 7B. For
Lao.2Y1.8O3, Nal, and Csl tested with Cs-137 and Co-60 (Figures 8A-8F), the values are as follows. The Lao.2Y1.sO3 sample tested had a volume of 0.07 cm3. The energy resolution for 5 μθ Cs-137 was 4.30% and the total number of counts is 37 cps (Figure 8A). The photo peaks for 1 μα Co-60 are not seen clearly, but bumps around 1.13 MeV and 1.36 MeV are detected (Figure 8B). Total number of counts is 50 cps. The Nal sample tested had a volume of 16.4 cm3. The energy resolution of the 0.662 MeV peak with Cs-137 is 4.14% and total counts is 12125 cps (Figure 8C). The energy resolution of the 1.17 MeV peak with Co-60 is 8.1%> and that of the 1.33 MeV is 4.02% (Figure 8D). Total number of counts is 14936 cps. The Csl sample tested had a volume of 1 cm3. The energy resolution with Cs-137 was 4.57%> and total number of counts was 227 cps (Figure 8E). The total number of counts with Co-60 was 21 cps (Figure 8F). Lao.2Y1.sO3 has an energy resolution comparable to that of Csl and Nal scintillators.
TABLE II provides the energy resolution and detection efficiency of an example of a disclosed scintillator, Lao.2Y1.sO3 when exposed to various sources of radioactivity.
TABLE II
1. four sources
2. without reflector
3. with reflector
4. four sources
TABLE III compares the energy resolution and detector efficiency of a disclosed scintillator with scintillators cesium iodide (Csl) and sodium iodide (Nal) using different sources of radiation.
TABLE III
2. METHODS
Disclosed herein are methods for detecting a source of radiation emitted from a radioactive element. Specifically The disclosure relates to lanthanum-yttrium oxide scintillators used for detecting radiation, such as X-rays, gamma rays, beta-rays, protons, electrons, and thermal neutron radiation and charged particles. The scintillators can be used for in security, medical imaging, particle physics, space, soil, and other applications.
In one aspect disclosed is a method for detecting the presence of a radioactive element or a source of radiation, comprising:
a) receiving radiation from a radiation source, the radiation impinging upon a
scintillator having the formula:
AxB2_x03
wherein A is chosen from La, Y, Lu or Sc;
B is chosen from La, Y, Lu or Sc;
provided that A and B are not the same element;
the index x is greater than 0 and less than 2 (0 < x < 2);
wherein the impinging radiation causes the scintillator to emit electromagnetic radiation; and
b) measuring the resulting electromagnetic emission.
In a further aspect disclosed is a method for detecting the presence of a radioactive element or a source of radiation, comprising:
a) receiving radiation from an ultraviolet radiation source, the radiation impinging upon a scintillator having the formula:
AxB2_x03
wherein A is chosen from La, Y, Lu or Sc;
B is chosen from La, Y, Lu or Sc;
provided that A and B are not the same element;
the index x is greater than 0 and less than 2 (0 < x < 2);
wherein the impinging radiation causes photoluminescence; and b) measuring the resulting photoluminescence.
In a yet further aspect disclosed is a method for detecting the presence of a radioactive element or a source of radiation , comprising:
a) receiving X-rays from an X-ray source, the X-rays impinging upon a scintillator having the formula:
AxB2_x03
wherein A is chosen from La, Y, Lu or Sc;
B is chosen from La, Y, Lu or Sc;
provided that A and B are not the same element;
the index x is greater than 0 and less than 2 (0 < x < 2);
wherein the impinging radiation causes the X-ray induced luminescence or fluorescence; and
b) measuring the resulting luminescence or fluorescence.
By the term "measuring" is meant either quantifying, qualifying the photoluminescence or providing both types of measurements. The wavelength of the emitted electromagnetic radiation can be used to qualify the source of radiation, for example, to correlate the wavelength of the emission with a particular source of radiation. Alternatively, the intensity of
the emission can be used to quantify the amount of radiation being received. The formulator can therefore utilize the disclosed scintillators to identify the source of the radiation, for example, the element or elements producing the radiation, as well as the relative amounts of each.
The term "impinge" and its various forms means to contact, strike, hit, collide with or otherwise make contact. For example, radiation impinges the scintillator when the radiation makes contact with the scintillator.
The term "electromagnetic radiation" as meant herein is used in the accepted scientific definition. An example of electromagnetic radiation includes visible light which is one resultant of photo luminescence.
In a further aspect disclosed is a method for detecting the presence of a source of radiation, comprising:
a) receiving radiation from a radiation source, the radiation impinging upon a scintillator comprising Lao.2Y1.sO3, wherein the impinging radiation causes the scintillator to photoluminescence; and
b) measuring the resulting photoluminescence.
In one embodiment of this aspect the method comprises:
a) receiving X-rays from a source of X-rays, the X-rays impinging upon a
scintillator comprising Lao.2Y1.sO3, wherein the impinging X-rays cause the scintillator to emit X-ray induced optical luminescence or X-ray fluorescence; and
b) measuring the resulting X-ray induced optical luminescence or X-ray
fluorescence.
The photoluminescence can be measured, quantified or qualified by any means chosen by the formulator. See Resch-Genger et al., "Characterization of photoluminescence measuring systems (IUPAC Technical Report)," Pure Appl. Chem., Vol. 84, No. 8, pp. 1815- 1835, (2012) for a discussion of photoluminescence detection.
3. DEVICES
Further disclosed herein is a device for detecting the presence of radiation, comprising: a) a scintillator having the formula:
AxB2_x03
wherein A is chosen from La, Y, Lu or Sc;
B is chosen from La, Y, Lu or Sc;
provided that A and B are not the same element;
the index x is greater than 0 and less than 2 (0 < x < 2); and
b) a detector for receiving emitted electromagnetic radiation.
In one aspect the scintillator is fabricated into a thin transparent or translucent glass onto which radiation impinges. The glass is configured with a detector which detects any electromagnetic radiation that is emitted by the scintillator and which is used to verify the presence of a radiation source. The electromagnetic radiation emitted by the scintillator can be photo luminescence, X-ray induced optical luminescence or X-ray fluorescence.
Also disclosed herein is the use of the disclosed scintillators for detecting the presence of suspected radiation. For example, within a security setting, a person trying to transport a source of radiation can be detected using the disclosed scintillators. In addition, cargo containers, packages, and the like can be examined for a hidden source of radiation.
Other advantages which are obvious and which are inherent to the invention will be evident to one skilled in the art. It will be understood that certain features and subcombinations are of utility and may be employed without reference to other features and subcombinations. This is contemplated by and is within the scope of the claims. Since many possible embodiments may be made of the invention without departing from the scope thereof, it is to be understood that all matter herein set forth or shown in the accompanying drawings is to be interpreted as illustrative and not in a limiting sense.
Claims
WHAT IS CLAIMED IS:
1. A method for detecting the presence of a radioactive element or a source of radiation, comprising:
a) receiving radiation from a radiation source, the radiation impinging upon a scintillator having the formula:
AxB2_x03
wherein A is an element chosen from La, Y, Lu or Sc;
B is an element chosen from La, Y, Lu or Sc;
provided that A and B are not the same element;
the index x is greater than 0 and less than 2 (0 < x < 2);
wherein the impinging radiation causes the scintillator to emit electromagnetic radiation; and
b) measuring the resulting electromagnetic emission.
2. The method according to Claim 1, wherein the radiation impinging upon the scintillator is from an ultraviolet source and the electromagnetic emission is photoluminescence.
3. The method according to Claim 1, wherein the radiation impinging upon the scintillator is from an X-ray source and the electromagnetic emission is X-ray induced
luminescence or fluorescence.
4. The method according to any one of Claims 1 to 3, wherein the scintillator has the formula LaxY2_x03.
5. The method according to any one of Claims 1 to 4, wherein the scintillator is chosen from La0.05Yi.95O3, La0.iYi.9O3; La0.2Yi.8O3; La0.3Yi.7O3; La0.4Yi.6O3; La0.5Yi.5O3; and
6. The method according to any one of Claims 1 to 5, wherein the scintillator has the formula Lao.2Yi.g03.
7. The method according to any one of Claims 1 to 3, wherein the scintillator has the formula LaxSc2_x03.
The method according to any one of Claims 1 to 3 and 7, wherein the scintillator chosen from Lao.05Sc1.95O3, La0.iSci.9O3; Lao.2Sc1.gO3; La0.3Sci.7O3; La0.4Sci.6O3;
La0.5Sci.5O3; and La0.6Sci.4O3.
9. The method according to any one of Claims 1 to 3, wherein the scintillator has the formula LaxLu2_x03.
The method according to any one of Claims 1 to 3 and 9, wherein the scintillator chosen from Lao.05Lu1.95O3, Lao.1Lu1.9O3; Lao.2Lu1.8O3; Lao.3Lui.703; Lao.4Lui.603 Lao.5Lu1.5O3; and Lao.6Lui.403.
11. A method for detecting the presence of a source of radiation, comprising:
a) receiving radiation from an ultraviolet radiation source, the radiation impinging upon a scintillator having the formula:
AxB2_x03
wherein A is chosen from La, Y, Lu or Sc;
B is chosen from La, Y, Lu or Sc;
provided that A and B are not the same element;
the index x is greater than 0 and less than 2 (0 < x < 2);
wherein the impinging radiation causes photoluminescence; and b) measuring the resulting photoluminescence.
A method for detecting the presence of a radioactive element or a source of radiation, comprising:
a) receiving X-rays from an X-ray source, the X-rays impinging upon a scintillator having the formula:
AxB2_x03
wherein A is chosen from La, Y, Lu or Sc;
B is chosen from La, Y, Lu or Sc;
provided that A and B are not the same element;
the index x is greater than 0 and less than 2 (0 < x < 2);
wherein the impinging radiation causes the X-ray induced luminescence or fluorescence; and
b) measuring the resulting luminescence or fluorescence.
13. The method according to any one of Claims 11 or 12, wherein the scintillator has the formula LaxY2_x03.
14. The method according to any one of Claims 11 to 13, wherein the scintillator is chosen from Lao.05Y1.95O3, Lao.1Y1.9O3; La0.2Yi.8O3; Lao.3Y1.7O3; La0.4Yi.6O3; Lao.5Y1.5O3; and
15. A device for detecting the presence of radiation, comprising:
a) a scintillator having the formula:
AxB2_x03
wherein A is chosen from La, Y, Lu or Sc;
B is chosen from La, Y, Lu or Sc;
provided that A and B are not the same element;
the index x is greater than 0 and less than 2 (0 < x < 2); and
b) a detector for receiving emitted electromagnetic radiation.
16. The device according to Claim 15, wherein the scintillator has the formula LaxY2_x03.
17. The device according to either Claim 15 or 16, wherein the scintillator is chosen from Lao.05Y1.95O3, Lao.1Y1.9O3; La0.2Yi.8O3; Lao.3Y1.7O3; La0.4Yi.6O3; Lao.5Y1.5O3; and
18. The device according to any one of Claims 15 to 17, wherein the scintillator has the formula Lao.2Y1.sO3.
19. The use of a scintillator for detecting the presence of suspected radiation, comprising: a scintillator having the formula:
AxB2_x03
wherein A is chosen from La, Y, Lu or Sc;
B is chosen from La, Y, Lu or Sc;
provided that A and B are not the same element;
the index x is greater than 0 and less than 2 (0 < x < 2).
20. The use according to Claim 19, wherein the scintillator has the formula LaxY2-x03.
21. The use according to either Claim 19 or 20, wherein the scintillator is chosen from
La0.05Yi. 5O3, La0.iYi.9O3; La0.2Yi.8O3; La0.3Yi.7O3; La0.4Yi.6O3; La0.5Yi.5O3; and
22. The use according to any one of Claims 19 to 21, wherein the scintillator has the
formula La0.2Yi.8O3.
23. The use according to any one of Claims 19 to 22, wherein the suspected radiation is in a container.
24. The use according to any one of Claims 19 to 22, wherein a person has possession of the suspected radiation.
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| US14/907,601 US9739897B2 (en) | 2013-07-29 | 2014-07-29 | Lanthanum-yttrium oxide scintillators and use thereof |
| US15/649,441 US10184079B2 (en) | 2013-07-29 | 2017-07-13 | Lanthanum-yttrium oxide scintillators and use thereof |
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| US201361859466P | 2013-07-29 | 2013-07-29 | |
| US61/859,466 | 2013-07-29 |
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| US15/649,441 Continuation-In-Part US10184079B2 (en) | 2013-07-29 | 2017-07-13 | Lanthanum-yttrium oxide scintillators and use thereof |
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| US4211758A (en) * | 1978-12-26 | 1980-07-08 | Gte Laboratories Incorporated | Ceramic compositions and articles prepared therefrom |
| US5213712A (en) * | 1992-02-10 | 1993-05-25 | General Electric Company | Lanthanum lutetium oxide phosphor with cerium luminescence |
| US6946300B2 (en) * | 2002-02-01 | 2005-09-20 | Control Screening, Llc | Multi-modal detection of explosives, narcotics, and other chemical substances |
| RU2389835C2 (en) * | 2004-11-08 | 2010-05-20 | Тохоку Текно Арч Ко., Лтд. | Pr-CONTAINING SCINTILLATION MONOCRYSTAL, METHOD OF MAKING SAID CRYSTAL, RADIATION DETECTOR AND INSPECTION DEVICE |
| US20110024634A1 (en) | 2009-08-03 | 2011-02-03 | Radiation Monitoring Devices, Inc. | ENRICHED CsLiLn HALIDE SCINTILLATOR |
| CN101665696B (en) * | 2009-09-25 | 2012-08-08 | 上海大学 | Preparation method of Eu3+-doped lanthanum oxide phosphor powder and transparent scintillation ceramics |
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