CN117431067A - Mn-doped enhanced ionizing radiation luminescent halide scintillator and preparation method and application thereof - Google Patents
Mn-doped enhanced ionizing radiation luminescent halide scintillator and preparation method and application thereof Download PDFInfo
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- 230000005865 ionizing radiation Effects 0.000 title claims abstract description 101
- 150000004820 halides Chemical class 0.000 title claims abstract description 78
- 238000002360 preparation method Methods 0.000 title claims abstract description 25
- 239000011572 manganese Substances 0.000 claims abstract description 142
- 238000000034 method Methods 0.000 claims abstract description 36
- 239000000203 mixture Substances 0.000 claims abstract description 29
- 239000000126 substance Substances 0.000 claims abstract description 28
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims abstract description 25
- 229910052748 manganese Inorganic materials 0.000 claims abstract description 25
- 238000001514 detection method Methods 0.000 claims abstract description 18
- 239000002245 particle Substances 0.000 claims abstract description 9
- 229910052706 scandium Inorganic materials 0.000 claims abstract description 5
- 229910052727 yttrium Inorganic materials 0.000 claims abstract description 5
- 239000013078 crystal Substances 0.000 claims description 69
- 239000010453 quartz Substances 0.000 claims description 38
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 38
- 239000002994 raw material Substances 0.000 claims description 27
- 239000000843 powder Substances 0.000 claims description 22
- 238000007689 inspection Methods 0.000 claims description 12
- 238000001816 cooling Methods 0.000 claims description 10
- 238000007789 sealing Methods 0.000 claims description 7
- 230000005251 gamma ray Effects 0.000 claims description 6
- 238000010438 heat treatment Methods 0.000 claims description 6
- 238000002844 melting Methods 0.000 claims description 6
- 230000008018 melting Effects 0.000 claims description 6
- 230000008569 process Effects 0.000 claims description 6
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- 239000000463 material Substances 0.000 abstract description 11
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- 238000000295 emission spectrum Methods 0.000 description 12
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 10
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 10
- NIPNSKYNPDTRPC-UHFFFAOYSA-N N-[2-oxo-2-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 NIPNSKYNPDTRPC-UHFFFAOYSA-N 0.000 description 10
- 230000005284 excitation Effects 0.000 description 9
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- IHCCLXNEEPMSIO-UHFFFAOYSA-N 2-[4-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]piperidin-1-yl]-1-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethanone Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)C1CCN(CC1)CC(=O)N1CC2=C(CC1)NN=N2 IHCCLXNEEPMSIO-UHFFFAOYSA-N 0.000 description 4
- 239000000155 melt Substances 0.000 description 4
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- DFGKGUXTPFWHIX-UHFFFAOYSA-N 6-[2-[4-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]piperazin-1-yl]acetyl]-3H-1,3-benzoxazol-2-one Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)N1CCN(CC1)CC(=O)C1=CC2=C(NC(O2)=O)C=C1 DFGKGUXTPFWHIX-UHFFFAOYSA-N 0.000 description 2
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- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 1
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- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
- C09K11/08—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials
- C09K11/77—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing rare earth metals
- C09K11/7704—Halogenides
- C09K11/7705—Halogenides with alkali or alkaline earth metals
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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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Abstract
The invention relates to a manganese doped enhanced ionizing radiation luminescent halide scintillator and a preparation method and application thereof, belonging to the technical field of scintillation materials. Aiming at the problems of poor luminous intensity, strong self-absorption and the like of ionizing radiation of the prior luminescent halide scintillator, the invention provides a manganese doped enhanced ionizing radiation luminescent halide scintillator, which has the chemical composition A 3 B 2‑y Mn y X 9 The method comprises the steps of carrying out a first treatment on the surface of the Wherein A is selected from one of Li, na, K, rb, cs; b is selected from one of Sc, Y, lu, la, gd; x is selected from one of F, cl, br, I; y is more than 0 and less than or equal to 0.4. The Mn-doped enhanced ionizing radiation luminescent halide scintillator has the advantages of high ionizing radiation luminous efficiency and the like, and can be used for detecting X-rays, gamma-rays and other rays or particle detection.
Description
Technical Field
The invention relates to a manganese doped enhanced ionizing radiation luminescent halide scintillator and a preparation method and application thereof, belonging to the technical field of scintillation materials.
Background
The scintillator is an energy converter capable of converting incident high-energy rays or high-energy particles into ultraviolet or visible light, is used as a core component of a radiation detector due to its own unique performance, and has great application value in the fields of high-energy physics, nuclear medicine imaging, homeland security, industrial detection and the like. The existing scintillator materials have limitations in ionizing radiation luminous efficiency, time resolution, energy resolution and the like, and limit further application of the scintillator materials in high-performance radiation detectors. Therefore, in order to meet the higher performance requirements of the scintillation detection materials in the fields of scientific research, medicine, industry and the like, which are increasingly different, the development of novel high-performance scintillation materials is urgent.
The zero-dimensional perovskite material breaks the connectivity between the octahedrons in the traditional perovskite material, and retains the photophysical properties of the octahedrons of the single metal halide. The reason for this luminescence is mostly due to the luminescence of self-trapping excitons (STE) of the halide polyhedra [ AXn ] m-. When the material is excited by light, a strong coupling effect is generated between electrons and phonons, so that the lattice transient state is distorted and the movement of the excitons in lattice points is broken, and the lattice self-traps, thereby forming self-trapped excitons. The trapped photogenerated electrons release energy in the form of a compound luminescence, ultimately exhibiting broad spectral emission and large stokes shift, with luminescence self-absorption thus being small or absent, which is a significant feature of STE luminescence. The carriers generated by photoexcitation are quantum confined in the isolated octahedra of the zero-dimensional perovskite, and the unique structure enables the zero-dimensional perovskite material to have longer exciton life and higher PLQY. When the atomic composition is different, the octahedron can generate different degrees of distortion, so that the zero-dimensional perovskite structure halide shows rich photoelectric characteristics, and has a great application potential in the field of radiation detection.
Cs of zero-dimensional structure grown by melt method 3 Cu 2 I 5 The light yield of the single crystal under 662keV gamma rays is 32,000 photons/MeV, which is far higher than that of 8,000 photons/MeV of the current commercial BGO; at the same time, cs 3 Cu 2 I 5 The energy resolution of the single crystal is about 5.3%, which is slightly inferior to the current commercial LaBr 3 3% of Ce. But it is notable that LaBr 3 Ce has high melting point, strong deliquescence and difficult processing, and Cs 3 Cu 2 I 5 The single crystal has a low melting point and is not deliquescent. For example A 3 RE 2 X 9 The lanthanide rare earth elements in the luminescent halide scintillator have [ Xe ]]4f n Electrons on the 4f orbit give it unique optical, electrical and magneto-physical properties, part of RE 3+ The 4f-5d transition of (2) shows broadband emission and shorter fluorescence lifetime, but is defined by A 3 RE 2 X 9 Non-radiative recombination induced by defective state energy levels in the band gap of the luminescent halide scintillator greatly reduces exciton trapping efficiency, resulting in poor ionizing radiation emission intensity.
Disclosure of Invention
Aiming at the problems of poor luminous intensity, strong self-absorption and the like of ionizing radiation of the existing luminous halide scintillator, the invention aims to provide a manganese doped enhanced ionizing radiation luminous halide scintillator, a preparation method and application thereof, and the scintillator can be widely applied to the field of radiation detection.
In a first aspect, the present invention provides a manganese doped enhanced ionizing radiation emitting halide scintillator having a chemical composition A 3 B 2-y Mn y X 9 ；
Wherein A is selected from one of Li, na, K, rb, cs;
b is selected from one of Sc, Y, lu, la, gd;
x is selected from one of F, cl, br, I;
0＜y≤0.4。
in the invention, a new luminescence center is introduced through Mn doping, the activity range of electrons is bound to a certain extent, the exciton capturing efficiency is improved in different ranges, and A is improved 3 RE 2 X 9 Probability of radiative recombination for a luminescent halide scintillator. Electron hole pairs excited by ionizing radiation migrate to Mn 2+ Nearby, post-relaxation hairRaw materials 4 T 1 → 6 A 1 The transition, the single emission source, the stable wavelength, realized the different degree improvement of ionizing radiation luminous intensity.
Preferably, B is La.
Preferably, y is more than or equal to 0.05 and less than or equal to 0.3; preferably, y is more than or equal to 0.08 and less than or equal to 0.15; more preferably, 0.09.ltoreq.y.ltoreq.0.12; most preferably y=0.1.
Preferably, the manganese doped enhanced ionizing radiation luminescent halide scintillator is in the form of a bulk single crystal; preferably, when the manganese doped enhanced ionizing radiation emitting halide scintillator is a bulk single crystal, the manganese doped enhanced ionizing radiation emitting halide scintillator is not less than 1 mm in size in at least one dimension.
In a second aspect, the present invention provides a method for producing a manganese-doped enhanced ionizing radiation emitting halide scintillator, when the manganese-doped enhanced ionizing radiation emitting halide scintillator is a bulk single crystal, the method comprising: enhancing the chemical composition A of the ionizing radiation-emitting halide scintillator according to the manganese doping 3 B 2-y Mn y X 9 The AX powder and the BX powder are respectively weighed according to the molar ratio 3 Powder and MnX 2 The powder is mixed and used as raw material powder; and growing to obtain the manganese doped enhanced ionizing radiation luminescent halide scintillator by adopting a Bridgman method.
Preferably, the AX powder and BX 3 Powder and MnX 2 The purity of the powder is over 99.9 percent.
Preferably, the parameters of the Bridgman method include:
(1) Placing raw material powder into a quartz crucible with a capillary tip structure, and sealing after vacuumizing;
(2) Vertically placing the quartz crucible in a crystal growth furnace, then heating to the melting point temperature of the raw material powder, and preserving heat to enable the raw material powder to be completely melted and fully mixed;
(3) Adjusting the height position and furnace temperature of the quartz crucible so that the temperature of the capillary tip structure of the quartz crucible is kept between +/-10 ℃ of the crystallization point of the manganese doped enhanced ionizing radiation luminescent halide scintillator;
(4) Controlling the longitudinal temperature gradient of the crystal growth furnace to be 5-50 ℃/cm, then enabling the quartz crucible to descend in the furnace body at the speed of 0.01-10.0 mm/h, and starting the growth of crystals;
(5) And after the growth is finished, cooling to room temperature.
Preferably, in the step (1), the size of the capillary tip structure in the quartz crucible with the capillary tip structure is 0-3 cm; in the step (5), the cooling rate for cooling to the room temperature is 0.5-50 ℃/h.
In a third aspect, the present invention provides the use of a manganese doped enhanced ionizing radiation emitting halide scintillator in X-ray detection, gamma ray detection and particle detection, including medical imaging, security inspection, petroleum exploration wells and industrial detection.
The invention has the beneficial effects that:
the manganese-doped enhanced ionizing radiation-based luminescent halide scintillator has the advantages of non (weak) deliquescence, high ionizing radiation luminous efficiency, no luminescence self-absorption and the like, can be used for detecting rays or particles such as X rays and gamma rays, and has important application prospects in the fields of medical imaging, security inspection, petroleum exploration wells, industrial detection and the like.
Drawings
FIG. 1 shows Cs in example 1 3 Y 1.9 Mn 0.1 Cl 9 Is a graph of the ionization radiation luminescence spectrum of (2);
FIG. 2 is a graph of Cs in example 2 3 Lu 1.9 Mn 0.1 Cl 9 Is a graph of the ionization radiation luminescence spectrum of (2);
FIG. 3 shows Cs in example 6 3 La 1.9 Mn 0.1 Cl 9 Is a graph of the ionization radiation luminescence spectrum of (2);
FIG. 4 shows Cs in example 12 3 Gd 1.9 Mn 0.1 Cl 9 Is a graph of the ionization radiation luminescence spectrum of (2);
FIG. 5 is Cs in comparative example 1 3 Y 2 Cl 9 And Cs in example 1 3 Y 1.9 Mn 0.1 Cl 9 Is a contrast chart of the ionization radiation luminescence spectrum of (a);
FIG. 6 is a graph of comparative example 2Cs 3 Lu 2 Cl 9 And Cs in example 2 3 Lu 1.9 Mn 0.1 Cl 9 Is a contrast chart of the ionization radiation luminescence spectrum of (a);
FIG. 7 shows Cs in comparative example 3 3 La 2 Cl 9 As with Cs in example 6 3 La 1.9 Mn 0.1 Cl 9 An ionizing radiation luminescence spectrum contrast plot of the ionizing radiation luminescent halide scintillator before and after manganese doping;
FIG. 8 is a graph showing Cs in comparative example 4 3 Gd 2 Cl 9 Cs as in example 12 3 Gd 1.9 Mn 0.1 Cl 9 Is a contrast chart of the ionization radiation luminescence spectrum of (a);
FIG. 9 is Cs in comparative example 3 3 La 2 Cl 9 Cs as in example 3 3 La 1.99 Mn 0.01 Cl 9 A contrast ionizing radiation luminescence spectrum;
FIG. 10 shows Cs in comparative example 3 3 La 2 Cl 9 Cs as in example 4 3 La 1.95 Mn 0.05 Cl 9 A contrast ionizing radiation luminescence spectrum;
FIG. 11 shows Cs in comparative example 3 3 La 2 Cl 9 Cs as in example 5 3 La 1.92 Mn 0.08 Cl 9 A contrast ionizing radiation luminescence spectrum;
FIG. 12 shows Cs in comparative example 3 3 La 2 Cl 9 Cs as in example 7 3 La 1.88 Mn 0.12 Cl 9 A contrast ionizing radiation luminescence spectrum;
FIG. 13 shows Cs in comparative example 3 3 La 2 Cl 9 Cs as in example 8 3 La 1.85 Mn 0.15 Cl 9 A contrast ionizing radiation luminescence spectrum;
FIG. 14 shows Cs in comparative example 3 3 La 2 Cl 9 Cs as in example 9 3 La 1.8 Mn 0.2 Cl 9 A contrast ionizing radiation luminescence spectrum;
FIG. 15 shows Cs in comparative example 3 3 La 2 Cl 9 Cs as in example 10 3 La 1.7 Mn 0.3 Cl 9 A contrast ionizing radiation luminescence spectrum;
FIG. 16 shows Cs in comparative example 3 3 La 2 Cl 9 Cs as in example 11 3 La 1.6 Mn 0.4 Cl 9 A contrast ionizing radiation luminescence spectrum;
FIG. 17 is Cs in comparative example 1 3 Y 2 Cl 9 Photoluminescence excitation and emission spectra of (a);
FIG. 18 shows Cs in example 1 3 Y 1.9 Mn 0.1 Cl 9 Photoluminescence excitation and emission spectra of (a);
FIG. 19 is a graph showing Cs in comparative example 2 3 Lu 2 Cl 9 Photoluminescence excitation and emission spectra of (a);
FIG. 20 shows Cs in example 2 3 Lu 1.9 Mn 0.1 Cl 9 Photoluminescence excitation and emission spectra of (c).
Detailed Description
The invention is further illustrated by the following embodiments, which are to be understood as merely illustrative of the invention and not limiting thereof.
In the present disclosure, the manganese doped enhanced ionizing radiation emitting halide scintillator has the formula A 3 B 2- y Mn y X 9 The method comprises the steps of carrying out a first treatment on the surface of the Wherein A is selected from one of Li, na, K, rb, cs; b is selected from one of Sc, Y, lu, la, gd; x is selected from one halogen element in F, cl, br, I; y is more than 0 and less than or equal to 0.4.
In an alternative embodiment, the manganese doped enhanced ionizing radiation emitting halide scintillator is in the form of a bulk single crystal.
The preparation method thereof is exemplarily described below. The invention can adopt Bridgman method to prepare blocky monocrystal. The preparation process is described in detail below by selecting only the Bridgman method as an example, and other crystal preparation methods are also applicable to the present invention.
According to the composition general formula A 3 B 2-y Mn y X 9 The molar ratio of each element is used for weighing each raw material and fullyMixing. In a glove box filled with dry argon or nitrogen, the starting materials were homogenized and transferred into a quartz crucible with a long haired structure (length about 2 cm); the crucible was evacuated to vacuum (about 10 -2 ～10 -7 Pa) and sealing by welding.
In an alternative embodiment, the feedstock comprises: high purity (more than or equal to 99.9%), anhydrous AX, high purity (more than or equal to 99.9%), anhydrous BX 3 High purity (more than or equal to 99.9 percent) and anhydrous MnX 2 The method comprises the steps of carrying out a first treatment on the surface of the Wherein: a= Li, na, K, rb and Cs; b= Sc, Y, lu, la and Gd; x=f, cl, br, and I; y is more than 0 and less than or equal to 0.4.
In an alternative embodiment, the sealed quartz crucible is transferred to a crucible holder for a period of time (e.g., 24 hours) and the crucible tightness is checked by a spark gun vacuum detector.
Vertically placing the welded quartz crucible or the quartz crucible subjected to vacuum inspection in the central position of a crystal growth furnace; raising the temperature of the crystal growing furnace to make the temperature exceed the melting point temperature of the raw materials with the highest melting point, and preserving the heat at the temperature until the raw materials are completely melted and fully mixed.
Regulating the height position and furnace temperature of the crucible to reduce the temperature of the capillary tip of the crucible to about the crystallization point of the scintillation crystal; ensures that the longitudinal temperature gradient of the growth furnace is 5-50 ℃/cm, and the quartz crucible descends in the furnace body at the speed of 0.01-10.0 mm/h. The crystal in the growth furnace nucleates at the capillary tip of the crucible and solidifies toward the tail until the melt is completely crystallized.
After the growth is finished, the growth furnace is cooled to room temperature at a cooling rate of 0.5-50 ℃/h; finally, the grown crystal is taken out from the quartz crucible.
In the invention, a tungsten target X-ray tube is adopted as an excitation source, and a QEpro spectrometer with ocean optics is adopted as a detector to test the ionization radiation luminescence of the obtained manganese doped enhanced ionization radiation luminescent halide scintillator. The manganese doping enhances the ionizing radiation luminous intensity of the ionizing radiation luminous halide scintillator to be 1.2-7 times of that of the undoped ionizing radiation luminous halide scintillator with the same component.
The present invention will be further illustrated by the following examples. It is also to be understood that the following examples are given solely for the purpose of illustration and are not to be construed as limitations upon the scope of the invention, since numerous insubstantial modifications and variations will now occur to those skilled in the art in light of the foregoing disclosure. The specific process parameters and the like described below are also merely examples of suitable ranges, i.e., one skilled in the art can make a suitable selection from the description herein and are not intended to be limited to the specific values described below.
Example 1:
the Mn-doped enhanced ionizing radiation emitting halide scintillator of example 1 is in the form of a bulk single crystal having a composition chemical formula of Cs 3 Y 1.9 Mn 0.1 Cl 9 I.e. as A 3 B 2-y Mn y X 9 Is of the general formula; a=cs; b=y; x=cl; y=0.1. The preparation method of the blocky monocrystal adopts the Bridgman method, and comprises the following steps:
a) The halide scintillator composition prepared in this example has the chemical formula Cs 3 Y 1.9 Mn 0.1 Cl 9 The high-purity raw materials CsCl and YCl with the purity of 99.9 percent and the total weight of 5g are respectively weighed according to the molar ratio 3 And MnCl 2 ；
b) In a glove box filled with argon or nitrogen, the raw materials were mixed uniformly and transferred into a quartz crucible with a capillary bottom of about 2 cm a; vacuumizing the crucible and sealing the crucible by welding;
c) Moving the sealed quartz crucible to a crucible frame and standing for 24 hours; performing contact inspection on the crucible by using a spark gun vacuum detector; the occurrence of glow discharge phenomenon indicates that the inside of the crucible is in a vacuum environment, and the crucible is successfully sealed;
d) Vertically placing the quartz crucible subjected to vacuum inspection in the central position inside a crystal growth furnace; heating the crystal growth furnace to enable the temperature to reach 800 ℃ from room temperature after 8 hours, and keeping the temperature for 24 hours to enable the raw materials to be completely melted and uniformly mixed; regulating the height position and furnace temperature of the crucible, reducing the temperature of the capillary tip of the crucible to about 720 ℃, then enabling the quartz crucible to descend relative to the furnace body at the speed of 0.5 mm/h, and nucleating crystals at the capillary tip of the crucible to descendGradually solidifying towards the tail end in the process until the melt is completely crystallized; then cooling to room temperature at a rate of 10 ℃/h; finally, the solidified halide scintillation crystal is removed from the quartz crucible in a dry environment and processed. The resulting Cs 3 Y 1.9 Mn 0.1 Cl 9 The halide scintillation crystal can be used in the fields of X-ray, gamma-ray and other rays or particle detection. The ionizing radiation emission spectrum shows that it has a highly efficient ionizing radiation emission property.
Example 2:
the Mn-doped enhanced ionizing radiation emitting halide scintillator of this example 2 is in the form of a bulk single crystal having a composition chemical formula of Cs 3 Lu 1.9 Mn 0.1 Cl 9 I.e. as A 3 B 2-y Mn y X 9 Is of the general formula; a=cs; b=lu; x=cl; y=0.1. The preparation method of the blocky single crystal by adopting the Bridgman method comprises the following steps:
a) The halide scintillator composition prepared in this example has the chemical formula Cs 3 Lu 1.9 Mn 0.1 Cl 9 The high-purity raw materials CsCl and LuCl with the purity of 99.9% and the total weight of 5g are respectively weighed according to the molar ratio 3 And MnCl 2 ；
b) In a glove box filled with argon or nitrogen, the raw materials were mixed uniformly and transferred into a quartz crucible with a capillary bottom of about 2 cm a; vacuumizing the crucible and sealing the crucible by welding;
c) Moving the sealed quartz crucible to a crucible frame and standing for 24 hours; performing contact inspection on the crucible by using a spark gun vacuum detector; the occurrence of glow discharge phenomenon indicates that the inside of the crucible is in a vacuum environment, and the crucible is successfully sealed;
d) Vertically placing the quartz crucible subjected to vacuum inspection in the central position inside a crystal growth furnace; heating the crystal growth furnace to enable the temperature to reach 980 ℃ from room temperature after 8 hours, and preserving the heat for 24 hours to enable the raw materials to be completely melted and uniformly mixed; regulating the height position and furnace temperature of the crucible, reducing the temperature of the capillary tip of the crucible to about 900 ℃, then lowering the quartz crucible relative to the furnace body at the speed of 0.5 mm/h, nucleating the crystal at the capillary tip of the crucible, and gradually solidifying towards the tail end in the lowering process until the meltCompletely crystallizing; then cooling to room temperature at a rate of 10 ℃/h; finally, the solidified halide scintillation crystal is removed from the quartz crucible in a dry environment and processed. The resulting Cs 3 Lu 1.9 Mn 0.1 Cl 9 The halide scintillation crystal can be used in the fields of X-ray, gamma-ray and other rays or particle detection. The ionizing radiation emission spectrum shows that it has a highly efficient ionizing radiation emission property.
Example 3:
the Mn-doped enhanced ionizing radiation emitting halide scintillator of example 3 is in the form of a bulk single crystal having a composition chemical formula of Cs 3 La 1.99 Mn 0.01 Cl 9 I.e. as A 3 B 2-y Mn y X 9 Is of the general formula; a=cs; b=la; x=cl; y=0.01. The preparation method of the blocky single crystal by adopting the Bridgman method comprises the following steps:
a) The halide scintillator composition prepared in this example has the chemical formula Cs 3 La 1.99 Mn 0.01 Cl 9 The high-purity raw materials CsCl and LaCl with the purity of 99.9 percent and the total weight of 5g are respectively weighed according to the molar ratio 3 And MnCl 2 ；
b) In a glove box filled with argon or nitrogen, the raw materials were mixed uniformly and transferred into a quartz crucible with a capillary bottom of about 2 cm a; vacuumizing the crucible and sealing the crucible by welding;
c) Moving the sealed quartz crucible to a crucible frame and standing for 24 hours; performing contact inspection on the crucible by using a spark gun vacuum detector; the occurrence of glow discharge phenomenon indicates that the inside of the crucible is in a vacuum environment, and the crucible is successfully sealed;
d) Vertically placing the quartz crucible subjected to vacuum inspection in the central position inside a crystal growth furnace; heating the crystal growth furnace to enable the temperature to reach 950 ℃ from room temperature after 8 hours, and preserving the heat for 24 hours to enable the raw materials to be completely melted and uniformly mixed; regulating the height position and furnace temperature of the crucible, reducing the temperature of the capillary tip of the crucible to about 850 ℃, then enabling the quartz crucible to descend relative to the furnace body at the speed of 0.5 mm/h, nucleating crystals at the capillary tip of the crucible, and gradually solidifying towards the tail end in the descending process until the melt is completely crystallized; then at a rate of 10 ℃/hThe rate is reduced to room temperature; finally, the solidified halide scintillation crystal is removed from the quartz crucible in a dry environment and processed. The resulting Cs 3 La 1.99 Mn 0.01 Cl 9 The halide scintillation crystal can be used in the fields of X-ray, gamma-ray and other rays or particle detection. The ionizing radiation emission spectrum shows that it has a highly efficient ionizing radiation emission property.
Example 4:
the Mn-doped enhanced ionizing radiation emitting halide scintillator of example 4 is in the form of a bulk single crystal having a composition chemical formula of Cs 3 La 1.95 Mn 0.05 Cl 9 I.e. as A 3 B 2-y Mn y X 9 Is of the general formula; a=cs; b=la; x=cl; y=0.05. The bulk single crystal described above was prepared by the Bridgman method, the preparation parameters of which are described in example 3.
Example 5:
the Mn-doped enhanced ionizing radiation emitting halide scintillator of this example 5 is in the form of a bulk single crystal having a composition chemical formula of Cs 3 La 1.92 Mn 0.08 Cl 9 I.e. as A 3 B 2-y Mn y X 9 Is of the general formula; a=cs; b=la; x=cl; y=0.08. The bulk single crystal described above was prepared by the Bridgman method, the preparation parameters of which are described in example 3.
Example 6:
the Mn-doped enhanced ionizing radiation emitting halide scintillator of example 6 is in the form of a bulk single crystal having a composition chemical formula of Cs 3 La 1.9 Mn 0.1 Cl 9 I.e. as A 3 B 2-y Mn y X 9 Is of the general formula; a=cs; b=la; x=cl; y=0.1. The bulk single crystal described above was prepared by the Bridgman method, the preparation parameters of which are described in example 3.
Example 7:
the Mn-doped enhanced ionizing radiation emitting halide scintillator of example 7 is in the form of a bulk single crystal having a composition chemical formula of Cs 3 La 1.88 Mn 0.12 Cl 9 I.e. as A 3 B 2-y Mn y X 9 Is of the general formula; a=cs; b=la; x=cl; y=0.12. The bulk single crystal described above was prepared by the Bridgman method, the preparation parameters of which are described in example 3.
Example 8:
the Mn-doped enhanced ionizing radiation emitting halide scintillator of example 8 is in the form of a bulk single crystal having a composition chemical formula of Cs 3 La 1.85 Mn 0.15 Cl 9 I.e. as A 3 B 2-y Mn y X 9 Is of the general formula; a=cs; b=la; x=cl; y=0.15. The bulk single crystal described above was prepared by the Bridgman method, the preparation parameters of which are described in example 3.
Example 9:
the Mn-doped enhanced ionizing radiation emitting halide scintillator of example 9 is in the form of a bulk single crystal having a composition chemical formula of Cs 3 La 1.8 Mn 0.2 Cl 9 I.e. as A 3 B 2-y Mn y X 9 Is of the general formula; a=cs; b=la; x=cl; y=0.2. The bulk single crystal described above was prepared by the Bridgman method, the preparation parameters of which are described in example 3.
Example 10:
the Mn-doped enhanced ionizing radiation emitting halide scintillator of example 10 is in the form of a bulk single crystal having a composition chemical formula of Cs 3 La 1.7 Mn 0.3 Cl 9 I.e. as A 3 B 2-y Mn y X 9 Is of the general formula; a=cs; b=la; x=cl; y=0.3. The bulk single crystal described above was prepared by the Bridgman method, the preparation parameters of which are described in example 3.
Example 11:
the Mn-doped enhanced ionizing radiation emitting halide scintillator of example 11 is a bulk single crystal having a composition chemical formula of Cs 3 La 1.6 Mn 0.4 Cl 9 I.e. as A 3 B 2-y Mn y X 9 Is of the general formula; a=cs; b=la; x=cl; y=0.4. The bulk single crystal described above was prepared by the Bridgman method, the preparation parameters of which are described in example 3.
Example 12:
the implementation isThe Mn-doped enhanced ionizing radiation emitting halide scintillator of example 12 is in the form of a bulk single crystal having a composition formula of Cs 3 Gd 1.9 Mn 0.1 Cl 9 I.e. as A 3 B 2-y Mn y X 9 Is of the general formula; a=cs; b=gd; x=cl; y=0.1. The preparation method of the blocky single crystal by adopting the Bridgman method comprises the following steps:
a) The halide scintillator composition prepared in this example has the chemical formula Cs 3 Gd 1.9 Mn 0.1 Cl 9 The high-purity raw materials CsCl and GdCl with the purity of 99.9 percent and the total weight of 5g are respectively weighed according to the molar ratio 3 And MnCl 2 ；
b) In a glove box filled with argon or nitrogen, the raw materials were mixed uniformly and transferred into a quartz crucible with a capillary bottom of about 2 cm a; vacuumizing the crucible and sealing the crucible by welding;
c) Moving the sealed quartz crucible to a crucible frame and standing for 24 hours; performing contact inspection on the crucible by using a spark gun vacuum detector; the occurrence of glow discharge phenomenon indicates that the inside of the crucible is in a vacuum environment, and the crucible is successfully sealed;
d) Vertically placing the quartz crucible subjected to vacuum inspection in the central position inside a crystal growth furnace; heating the crystal growth furnace to reach 700 ℃ from room temperature after 8 hours, and preserving heat for 24 hours to completely melt and mix the raw materials uniformly; regulating the height position and furnace temperature of the crucible, reducing the temperature of the capillary tip of the crucible to about 600 ℃, then enabling the quartz crucible to descend relative to the furnace body at the speed of 0.5 mm/h, nucleating crystals at the capillary tip of the crucible, and gradually solidifying towards the tail end in the descending process until the melt is completely crystallized; then cooling to room temperature at a rate of 10 ℃/h; finally, the solidified halide scintillation crystal is removed from the quartz crucible in a dry environment and processed. The resulting Cs 3 Gd 1.9 Mn 0.1 Cl 9 The halide scintillation crystal can be used in the fields of X-ray, gamma-ray and other rays or particle detection. The ionizing radiation emission spectrum shows that it has a highly efficient ionizing radiation emission property.
Comparative example 1:
the rare earth halide of comparative example 1 was in the form of a blockSingle crystal of the form and the chemical formula of the composition is Cs 3 Y 2 Cl 9 The preparation is described in example 1. The only differences are: in step a), as halide Cs 3 Y 2 Cl 9 The molar ratio of each element in the chemical formula is respectively measured to obtain high-purity raw materials CsCl and YCl with the purity of 99.9 percent 3 The method comprises the steps of carrying out a first treatment on the surface of the By comparison, cs 3 Y 2 Cl 9 Exhibit a higher Cs under ionizing radiation 3 Y 1.9 Mn 0.1 Cl 9 Weak luminous intensity of ionizing radiation, cs 3 Y 1.9 Mn 0.1 Cl 9 The luminous intensity is about Cs 3 Y 2 Cl 9 1.7 times of (2).
Comparative example 2:
the rare earth halide of comparative example 2, which is in the form of bulk single crystal, has a composition chemical formula of Cs 3 Lu 2 Cl 9 The preparation is described in example 2. The only differences are: in step a), as halide Cs 3 Lu 2 Cl 9 The molar ratio of each element in the chemical formula is respectively measured to obtain high-purity raw materials CsCl and LuCl with the purity of 99.9 percent 3 The method comprises the steps of carrying out a first treatment on the surface of the By comparison, cs 3 Lu 2 Cl 9 Exhibit a higher Cs under ionizing radiation 3 Lu 1.9 Mn 0.1 Cl 9 Weak luminous intensity of ionizing radiation, cs 3 Lu 1.9 Mn 0.1 Cl 9 The luminous intensity is about Cs 3 Lu 2 Cl 9 Is 2.8 times as large as the above.
Comparative example 3:
the rare earth halide of comparative example 3, which is in the form of bulk single crystal, has a composition chemical formula of Cs 3 La 2 Cl 9 See example 5 for its preparation. The only differences are: in step a), as halide Cs 3 La 2 Cl 9 The molar ratio of each element in the chemical formula is respectively measured to obtain high-purity raw materials CsCl and LaCl with the purity of 99.9 percent 3 The method comprises the steps of carrying out a first treatment on the surface of the By comparison, cs 3 La 2 Cl 9 Exhibit a higher Cs under ionizing radiation 3 La 1.9 Mn 0.1 Cl 9 Weak luminous intensity of ionizing radiation, cs 3 La 1.9 Mn 0.1 Cl 9 The luminous intensity is about Cs 3 La 2 Cl 9 Is 6.8 times as large as the above.
Comparative example 4:
the rare earth halide of comparative example 4, which is in the form of bulk single crystal, has a composition chemical formula of Cs 3 Gd 2 Cl 9 The preparation is described in example 9. The only differences are: in step a), as halide Cs 3 Gd 2 Cl 9 The molar ratio of each element in the chemical formula is respectively measured to obtain high-purity raw materials CsCl and GdCl with the purity of 99.9 percent 3 The method comprises the steps of carrying out a first treatment on the surface of the By comparison, cs 3 Gd 2 Cl 9 Exhibit a higher Cs under ionizing radiation 3 Gd 1.9 Mn 0.1 Cl 9 Weak luminous intensity of ionizing radiation, cs 3 Gd 1.9 Mn 0.1 Cl 9 The luminous intensity is about Cs 3 Gd 2 Cl 9 1.7 times of (2).
Table 1 shows the composition and performance parameters of the prepared halide scintillators:
。
FIG. 1 shows Cs in example 1 3 Y 1.9 Mn 0.1 Cl 9 Is a graph of the ionization radiation luminescence spectrum of (2). As shown in FIG. 1, cs 3 Y 1.9 Mn 0.1 Cl 9 The ionization radiation luminescence with high efficiency under the radiation is shown, and two emission centers are respectively positioned at 300-550-nm and 550-800 nm.
FIG. 2 is Cs in example 2 3 Lu 1.9 Mn 0.1 Cl 9 Is a graph of the ionization radiation luminescence spectrum of (2). As shown in FIG. 2, cs 3 Lu 1.9 Mn 0.1 Cl 9 Exhibits high-efficiency ionizing radiation luminescence at 600-800 nm under irradiation.
FIG. 3 is Cs in example 6 3 La 1.9 Mn 0.1 Cl 9 Is a graph of the ionization radiation luminescence spectrum of (2). As shown in FIG. 3, cs 3 La 1.9 Mn 0.1 Cl 9 The ionization radiation luminescence with high efficiency is shown under the radiation, and three emission centers are respectively positioned at 220-320 nm, 320-530 nm and 530-700 nm.
FIG. 4 shows Cs in example 12 3 Gd 1.9 Mn 0.1 Cl 9 Is a graph of the ionization radiation luminescence spectrum of (2). As shown in FIG. 4, cs 3 Gd 1.9 Mn 0.1 Cl 9 Exhibits high-efficiency ionizing radiation luminescence at 300-320 nm, 350-530 nm and 530-800 nm under irradiation.
FIG. 5 shows Cs in comparative example 1 3 Y 2 Cl 9 Cs as in example 1 3 Y 1.9 Mn 0.1 Cl 9 Is a graph of the luminescence spectrum of ionizing radiation. As shown in FIG. 5, cs 3 Y 2 Cl 9 Under irradiation compared with Cs 3 Y 1.9 Mn 0.1 Cl 9 Exhibits weak ionizing radiation luminescence, cs 3 Y 1.9 Mn 0.1 Cl 9 Intensity of about Cs 3 Y 2 Cl 9 1.7 times of (2).
FIG. 6 is Cs in comparative example 2 3 Lu 2 Cl 9 Cs as in example 2 3 Lu 1.9 Mn 0.1 Cl 9 Is a contrast ionization radiation luminescence spectrum. As shown in FIG. 6, cs 3 Lu 2 Cl 9 Under irradiation compared with Cs 3 Lu 1.9 Mn 0.1 Cl 9 Exhibits a weak luminescence by ionizing radiation, cs 3 Lu 1.9 Mn 0.1 Cl 9 Intensity of about Cs 3 Lu 2 Cl 9 Is 2.8 times as large as the above.
FIG. 7 is Cs in comparative example 3 3 La 2 Cl 9 Cs as in example 6 3 La 1.9 Mn 0.1 Cl 9 Is a contrast ionization radiation luminescence spectrum. As shown in FIG. 7, cs 3 La 2 Cl 9 Under irradiation compared with Cs 3 La 1.9 Mn 0.1 Cl 9 Exhibits a weak luminescence by ionizing radiation, cs 3 La 1.9 Mn 0.1 Cl 9 Intensity of about Cs 3 La 2 Cl 9 Is 6.8 times as large as the above.
FIG. 8 is Cs in comparative example 4 3 Gd 2 Cl 9 Cs as in example 12 3 Gd 1.9 Mn 0.1 Cl 9 Is a graph of the luminescence spectrum of ionizing radiation. As shown in FIG. 8, cs 3 Gd 2 Cl 9 Under irradiation compared with Cs 3 Gd 1.9 Mn 0.1 Cl 9 Exhibits weak ionizing radiation luminescence, cs 3 Gd 1.9 Mn 0.1 Cl 9 Is about Cs in strength 3 Gd 2 Cl 9 1.7 times of (2).
FIG. 9 is Cs in comparative example 3 3 La 2 Cl 9 Cs as in example 3 3 La 1.99 Mn 0.01 Cl 9 Is a contrast ionization radiation luminescence spectrum. As shown in FIG. 9, cs 3 La 2 Cl 9 Under irradiation compared with Cs 3 La 1.99 Mn 0.01 Cl 9 Exhibits a weak luminescence by ionizing radiation, cs 3 La 1.99 Mn 0.01 Cl 9 Intensity of about Cs 3 La 2 Cl 9 1.5 times of (2).
FIG. 10 shows Cs in comparative example 3 3 La 2 Cl 9 Cs as in example 4 3 La 1.95 Mn 0.05 Cl 9 Is a contrast ionization radiation luminescence spectrum. As shown in FIG. 10, cs 3 La 2 Cl 9 Under irradiation compared with Cs 3 La 1.95 Mn 0.05 Cl 9 Exhibits a weak luminescence by ionizing radiation, cs 3 La 1.95 Mn 0.05 Cl 9 Intensity of about Cs 3 La 2 Cl 9 1.6 times of (2).
FIG. 11 shows Cs in comparative example 3 3 La 2 Cl 9 Cs as in example 5 3 La 1.92 Mn 0.08 Cl 9 Is a contrast ionization radiation luminescence spectrum. As shown in FIG. 11, cs 3 La 2 Cl 9 Under irradiation compared with Cs 3 La 1.92 Mn 0.08 Cl 9 Exhibits a weak luminescence by ionizing radiation, cs 3 La 1.92 Mn 0.08 Cl 9 Intensity of about Cs 3 La 2 Cl 9 4.4 times of (a).
FIG. 12 shows Cs in comparative example 3 3 La 2 Cl 9 Cs as in example 7 3 La 1.88 Mn 0.12 Cl 9 Is a contrast ionization radiation luminescence spectrum. As shown in FIG. 12, cs 3 La 2 Cl 9 Under irradiation compared with Cs 3 La 1.88 Mn 0.12 Cl 9 Exhibits a weak luminescence by ionizing radiation, cs 3 La 1.88 Mn 0.12 Cl 9 Intensity of about Cs 3 La 2 Cl 9 Is 5.3 times as large as the above.
FIG. 13 shows Cs in comparative example 3 3 La 2 Cl 9 Cs as in example 8 3 La 1.85 Mn 0.15 Cl 9 Is a contrast ionization radiation luminescence spectrum. As shown in FIG. 13, cs 3 La 2 Cl 9 Under irradiation compared with Cs 3 La 1.85 Mn 0.15 Cl 9 Exhibits a weak luminescence by ionizing radiation, cs 3 La 1.85 Mn 0.15 Cl 9 Intensity of about Cs 3 La 2 Cl 9 3.8 times of (3).
FIG. 14 shows Cs in comparative example 3 3 La 2 Cl 9 Cs as in example 9 3 La 1.8 Mn 0.2 Cl 9 Is a contrast ionization radiation luminescence spectrum. As shown in FIG. 14, cs 3 La 2 Cl 9 Under irradiation compared with Cs 3 La 1.8 Mn 0.2 Cl 9 Exhibits a weak luminescence by ionizing radiation, cs 3 La 1.9 Mn 0.1 Cl 9 Intensity of about Cs 3 La 2 Cl 9 Is 2.7 times as large as the above.
FIG. 15 shows Cs in comparative example 3 3 La 2 Cl 9 Cs as in example 10 3 La 1.7 Mn 0.3 Cl 9 Is a contrast ionization radiation luminescence spectrum. As shown in FIG. 15, cs 3 La 2 Cl 9 Under irradiation compared with Cs 3 La 1.7 Mn 0.3 Cl 9 Exhibits a weak luminescence by ionizing radiation, cs 3 La 1.9 Mn 0.1 Cl 9 Intensity of about Cs 3 La 2 Cl 9 2.2 times of (2).
FIG. 16 shows Cs in comparative example 3 3 La 2 Cl 9 Cs as in example 11 3 La 1.6 Mn 0.4 Cl 9 Is a contrast ionization radiation luminescence spectrum. As shown in FIG. 16, cs 3 La 2 Cl 9 Under irradiation compared with Cs 3 La 1.6 Mn 0.4 Cl 9 Exhibits a weak luminescence by ionizing radiation, cs 3 La 1.9 Mn 0.1 Cl 9 Intensity of about Cs 3 La 2 Cl 9 1.2 times of (2).
FIG. 17 is Cs in comparative example 1 3 Y 2 Cl 9 FIG. 18 shows the photoluminescence excitation and emission spectra of Cs in example 1 3 Y 1.9 Mn 0.1 Cl 9 Photoluminescence excitation and emission spectra of (c). As shown in fig. 17 and 18, cs 3 Y 2 Cl 9 Under fluorescence compared with Cs 3 Y 1.9 Mn 0.1 Cl 9 Exhibit a short Stokes shift, cs 3 Y 1.9 Mn 0.1 Cl 9 About ratio Cs of stokes shift of (c) 3 Y 2 Cl 9 15 nanometers long.
FIG. 19 is a graph showing Cs in comparative example 2 3 Lu 2 Cl 9 FIG. 20 shows the photoluminescence excitation and emission spectra of Cs in example 2 3 Lu 1.9 Mn 0.1 Cl 9 Photoluminescence excitation and emission spectra of (c). As shown in FIGS. 19 and 20, cs 3 Lu 2 Cl 9 Under fluorescence compared with Cs 3 Lu 1.9 Mn 0.1 Cl 9 Exhibit a short Stokes shift, cs 3 Lu 1.9 Mn 0.1 Cl 9 About ratio Cs of stokes shift of (c) 3 Lu 2 Cl 9 And 20 nanometers long.
Finally, what is necessary here is: the above embodiments are only for further detailed description of the technical solutions of the present invention, and should not be construed as limiting the scope of the present invention, and some insubstantial modifications and adjustments made by those skilled in the art from the above description of the present invention are all within the scope of the present invention.
Claims (13)
1. A manganese-doped enhanced ionizing radiation emitting halide scintillator is characterized in that the chemical composition of the manganese-doped enhanced ionizing radiation emitting halide scintillator is A 3 B 2-y Mn y X 9 ；
Wherein A is selected from one of Li, na, K, rb, cs;
b is selected from one of Sc, Y, lu, la, gd;
x is selected from one of F, cl, br, I;
0＜y≤0.4。
2. the manganese-doped enhanced ionizing radiation emitting halide scintillator of claim 1, wherein B is La.
3. The manganese-doped enhanced ionizing radiation emitting halide scintillator of claim 1, wherein y is 0.05-0.3.
4. The manganese-doped enhanced ionizing radiation emitting halide scintillator of claim 3, wherein y is 0.08-0.15.
5. The manganese-doped enhanced ionizing radiation emitting halide scintillator of claim 4, wherein y is 0.09 and 0.12.
6. The manganese doped enhanced ionizing radiation emitting halide scintillator of claim 5, wherein y = 0.1.
7. The manganese-doped enhanced ionizing radiation emitting halide scintillator of any one of claims 1 to 6, wherein the manganese-doped enhanced ionizing radiation emitting halide scintillator is in the form of a bulk single crystal.
8. The manganese doped enhanced ionizing radiation emitting halide scintillator of claim 7, wherein when the manganese doped enhanced ionizing radiation emitting halide scintillator is a bulk single crystal, the manganese doped enhanced ionizing radiation emitting halide scintillator is not less than 1 mm in at least one dimension.
9. A method of preparing the manganese-doped enhanced ionizing radiation emitting halide scintillator according to any one of claims 1 to 8, wherein when the manganese-doped enhanced ionizing radiation emitting halide scintillator is a bulk single crystal, the method of preparing comprises: enhancing the chemical composition A of the ionizing radiation-emitting halide scintillator according to the manganese doping 3 B 2-y Mn y X 9 The AX powder and the BX powder are respectively weighed according to the molar ratio 3 Powder and MnX 2 The powder is mixed and used as raw material powder; and growing to obtain the manganese doped enhanced ionizing radiation luminescent halide scintillator by adopting a Bridgman method.
10. The preparation method according to claim 9, wherein the AX powder body and BX are 3 Powder and MnX 2 The purity of the powder is over 99.9 percent.
11. The method according to claim 9, wherein the parameters of the bridgman process include:
(1) Placing raw material powder into a quartz crucible with a capillary tip structure, and sealing after vacuumizing;
(2) Vertically placing the quartz crucible in a crystal growth furnace, then heating to the melting point temperature of the raw material powder, and preserving heat to enable the raw material powder to be completely melted and fully mixed;
(3) Adjusting the height position and furnace temperature of the quartz crucible so that the temperature of the capillary tip structure of the quartz crucible is kept between +/-10 ℃ of the crystallization point of the manganese doped enhanced ionizing radiation luminescent halide scintillator;
(4) Controlling the longitudinal temperature gradient of the crystal growth furnace to be 5-50 ℃/cm, then enabling the quartz crucible to descend in the furnace body at the speed of 0.01-10.0 mm/h, and starting the growth of crystals;
(5) And after the growth is finished, cooling to room temperature.
12. The method of claim 11, wherein in step (1), the capillary tip structure in the quartz crucible having a capillary tip structure has a size of 0 to 3 cm;
in the step (5), the cooling rate for cooling to the room temperature is 0.5-50 ℃/h.
13. Use of a manganese doped enhanced ionizing radiation emitting halide scintillator according to any one of claims 1-8 in X-ray detection, gamma ray detection and particle detection, including medical imaging, security inspection, petroleum exploration wells and industrial detection.
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