CN117603690A - Multicomponent near infrared halide scintillation crystal - Google Patents
Multicomponent near infrared halide scintillation crystal Download PDFInfo
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- 239000013078 crystal Substances 0.000 title claims abstract description 76
- 150000004820 halides Chemical class 0.000 title claims abstract description 24
- LYQFWZFBNBDLEO-UHFFFAOYSA-M caesium bromide Chemical compound [Br-].[Cs+] LYQFWZFBNBDLEO-UHFFFAOYSA-M 0.000 claims abstract description 60
- 239000000843 powder Substances 0.000 claims abstract description 38
- 239000002994 raw material Substances 0.000 claims abstract description 27
- 230000006911 nucleation Effects 0.000 claims abstract description 19
- 238000010899 nucleation Methods 0.000 claims abstract description 19
- 230000002269 spontaneous effect Effects 0.000 claims abstract description 19
- 238000000034 method Methods 0.000 claims abstract description 12
- 230000005284 excitation Effects 0.000 claims abstract description 10
- 238000001514 detection method Methods 0.000 claims abstract description 8
- 238000003384 imaging method Methods 0.000 claims abstract description 4
- 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
- 238000002156 mixing Methods 0.000 claims description 14
- 238000007789 sealing Methods 0.000 claims description 11
- 238000010438 heat treatment Methods 0.000 claims description 10
- 239000000203 mixture Substances 0.000 claims description 3
- 229910052684 Cerium Inorganic materials 0.000 claims 1
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 claims 1
- 238000002844 melting Methods 0.000 claims 1
- 230000008018 melting Effects 0.000 claims 1
- 239000002245 particle Substances 0.000 claims 1
- 239000000919 ceramic Substances 0.000 description 9
- 238000005520 cutting process Methods 0.000 description 9
- 230000000694 effects Effects 0.000 description 9
- 238000000227 grinding Methods 0.000 description 9
- 238000005498 polishing Methods 0.000 description 9
- 239000012299 nitrogen atmosphere Substances 0.000 description 8
- 238000006243 chemical reaction Methods 0.000 description 7
- 238000004020 luminiscence type Methods 0.000 description 6
- 238000000098 azimuthal photoelectron diffraction Methods 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 238000002189 fluorescence spectrum Methods 0.000 description 3
- 230000005855 radiation Effects 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 239000012298 atmosphere Substances 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 238000000295 emission spectrum Methods 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 238000012546 transfer Methods 0.000 description 2
- 101100496858 Mus musculus Colec12 gene Proteins 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 238000006073 displacement reaction Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000002284 excitation--emission spectrum Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 238000009206 nuclear medicine Methods 0.000 description 1
- 238000005025 nuclear technology Methods 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
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- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
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- C09K11/77—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing rare earth metals
- C09K11/7766—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing rare earth metals containing two or more rare earth metals
- C09K11/7772—Halogenides
- C09K11/7773—Halogenides with alkali or alkaline earth metal
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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
- 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 provides a Ce 3+ 、Sm 2+ Doped multicomponent near infrared halide scintillation crystals having the formula Cs 2 LiLa 1‑x‑y Ce x Sm y Br 6 The method comprises the steps of carrying out a first treatment on the surface of the Wherein x has a value of 0<x is less than or equal to 0.1, and y is more than 0 and less than or equal to 0.05. CsBr powder, liBr powder and LaBr 3 Powder, ceBr 3 Powder and SmBr 2 The powder is prepared according to the molar ratio of 2:1 (1-x) x:y, and the Cs is grown by a spontaneous nucleation crucible descent method as raw material powder after being fully mixed 2 LiLa 1‑x Ce x Br 6 :ySm 2+ Multicomponent near infrared halide scintillation crystals. The crystal excitation peak is between 200nm and 300nm, and can emit 600-900nm broadband red light after excitation, and the crystal can be well applied to the near infrared and high-energy ray detection and imaging fields.
Description
Technical Field
The invention relates to the technical field of artificial scintillation crystals, in particular to a multi-component near-infrared halide scintillation crystal.
Background
With the development of technology and the wide application of nuclear technology, the technology is more and more paid attention to nuclear safety protection, nuclear diffusion, nuclear leakage, homeland safety, environmental nuclear radiation detection and the like. To the point ofMany scintillation crystals have been studied and put into use to date. The scintillation crystal itself cannot realize the conversion from optical signals to electrical signals, and the photoelectric conversion device is required to be matched. Photomultiplier tube (photomultiplier tube, abbreviated PMT) is an earlier-occurring photoelectric conversion device with an optimal response wavelength around 400 nm. The matching degree of the luminescence wavelength of the scintillation crystal and the optimal response wavelength of the photoelectric conversion device and the quantum efficiency of the photoelectric conversion device determine the performance of the scintillation crystal detector to a great extent. Therefore, the emission band of a large number of commercial scintillation crystals is matched with the detection sensitive area of PMT, such as NaI: tl (410 nm), laBr 3 :Ce(380nm)，SrI 2 Eu (435 nm), etc. With the recent development of photoelectric conversion devices, photoelectric conversion devices such as avalanche photodiodes (avalanche photodiode, abbreviated as APDs) having an optimal response wavelength range in the red-near infrared have appeared. The quantum efficiency of the avalanche photodiode can reach 80% or even more than 98% in the wave band of 700-800nm, and the quantum efficiency is improved by more than 2 times compared with a photomultiplier with the highest quantum efficiency of about 30%.
And Sm 2+ The luminescence band of the doped scintillation crystal is substantially concentrated in the long-wave region, e.g. Sm doped SrCl 2 (680nm)，CsYbBr 3 (810nm)，CsYbI 3 (820 nm), which matches well with the adapted band of APD. Theoretically, if the quantum efficiency of APD reaches 98% at the highest, the scintillator light yield reaches 62000 photon/MeV, which can achieve 2% excellent energy resolution at 662 keV. Whereas in view of the single Sm doping 2+ In recent years, the use of other ions as sensitizers has become a relatively broad improvement, such as Yb 2+ 、Eu 2+ Etc. These ions can transfer the energy captured from the ionization trajectory to Sm 2+ And light emission is completed. Therefore, the invention aims to take the scintillation crystal with the multicomponent elpasolite structure as the matrix material and select Ce 3+ As a sensitizer, the Ce-Sm energy transfer is used for realizing high-efficiency near-infrared luminescence, so that the novel near-infrared scintillation crystal with excellent performance is obtained.
Cs prepared by the invention 2 LiLa 1-x-y Ce x Sm y Br 6 The single crystal emission peak was located near 827 nm. The crystal is expected to be a high-performance multi-component near infrared halide scintillation crystal with good avalanche photodiode Guan Pipei.
Disclosure of Invention
In view of the above technical background, an object of the present invention is to provide a Ce 3+ 、Sm 2+ Co-doped multicomponent near infrared halide scintillation crystals and methods of making the same. The crystal has larger Stokes shift, suppresses the self-absorption problem of the crystal, and obtains high light output and good energy resolution. Can meet the wide application requirements of radiation detection technologies such as nuclear medicine, safety detection, X-ray imaging and the like.
The invention provides a multicomponent Ce 3+ ，Sm 2+ Doped multicomponent near infrared halide scintillation crystals having the formula Cs 2 LiLa 1-x-y Ce x Sm y Br 6 X is more than 0 and less than or equal to 0.1, and y is more than 0 and less than or equal to 0.05.
The Ce is 3+ 、Sm 2+ The doped multicomponent near infrared halide scintillation crystal emits near infrared light with the emission wavelength of 650-900nm under the excitation of 280nm light source, and near infrared light with the emission center of 827nm is obtained.
The invention also provides the Ce 3+ 、Sm 2+ A method of preparing a doped multicomponent near infrared halide scintillation crystal comprising: will CsBr, liBr, laBr 3 、CeBr 3 And SmBr 2 The powder is prepared by mixing x and y according to the molar ratio of 2:1 (1-x-y), wherein x is more than 0 and less than or equal to 0.1, y is more than 0 and less than or equal to 0.05, and the raw material powder is fully mixed to be used as raw material powder, and the Cs is grown by using the raw material powder through a crucible descent method, a pulling method and a kyropoulos method 2 LiLa 1-x-y Ce x Sm y Br 6 A scintillation crystal.
Another aspect of the invention provides Ce according to the invention 3+ 、Sm 2+ Use of doped multicomponent near infrared halide scintillation crystals wherein the Ce 3+ 、Sm 2+ Co-doped multicomponent near infrared halide scintillation crystal in near infrared and high energyUse in the field of radiation detection.
Drawings
FIG. 1 shows examples 2 to 4Ce 3+ 、Sm 2+ Doped multicomponent near infrared halide scintillation crystal physical photographs.
FIG. 2 is a sample of example 2Cs 2 LiLa 0.97 Ce 0.02 Sm 0.01 Br 6 Scintillation crystal, example 3Cs 2 LiLa 0.95 Ce 0.02 Sm 0.03 Br 6 Scintillation crystal, example 4Cs 2 LiLa 0.93 Ce 0.02 Sm 0.05 Br 6 Fluorescent spectrum diagram of scintillation crystal.
FIG. 3 is a sample of example 2Cs 2 LiLa 0.97 Ce 0.02 Sm 0.01 Br 6 Scintillation crystal, example 3Cs 2 LiLa 0.95 Ce 0.02 Sm 0.03 Br 6 Scintillation crystal, example 4Cs 2 LiLa 0.93 Ce 0.02 Sm 0.05 Br 6 The X-ray excitation emission spectrum of the scintillation crystal is shown.
Detailed Description
The invention is further described below with reference to the drawings and the following embodiments. It should be understood that the drawings and embodiments are only for illustrating the invention and are not to be construed as limiting the invention.
The invention is realized by researching Cs 2 LiLa 1-x-y Ce x Sm y Br 6 A multi-component near infrared halide scintillation crystal is developed, and a novel scintillation crystal material meeting the application requirements of high-energy ray detection and imaging is developed. The invention utilizes Sm 2+ Excellent light-emitting property, improved Ce 3+ The crystal with the doped elpasolite structure has the problems of small Stokes displacement, self absorption and the like, and obtains a new generation of high-performance Ce which can be used for near infrared emission 3+ 、Sm 2+ A co-doped multicomponent near infrared halide scintillation crystal. CsBr, liBr, laBr by 3 、CeBr 3 And SmBr 2 The powder is used as raw material to prepare Cs 2 LiLa 1-x-y Ce x Sm y Br 6 A multi-component near infrared halide scintillation crystal, wherein x is more than 0 and less than or equal to 0.1, and y is more than 0 and less than or equal to 0.05.
The preparation method comprises the following steps:
raw material powder material: csBr, liBr, laBr is put into a glove box with protective atmosphere 3 、CeBr 3 And SmBr 2 The powder is prepared by mixing x and y according to the molar ratio of 2:1 (1-x-y), wherein x is more than 0 and less than or equal to 0.1, y is more than 0 and less than or equal to 0.05, fully mixing, filling the mixture into a quartz or platinum crucible as raw material powder, and sealing under vacuum or anaerobic condition for later use. The raw material powder is preferably a high-purity powder, for example, 99.99% or more, preferably 99.999% or more.
Crystal growth: the crystal growth is carried out by Bridgman method (i.e. crucible descending method), the growth atmosphere is vacuum or anaerobic, the crystal growth speed is controlled to be 0.1-1mm/h, and the temperature gradient of the growth interface is 15-40 ℃/mm.
The invention is further illustrated by the following examples to better illustrate the invention. It is to be understood that the following examples are given solely for the purpose of illustration and are not to be construed as limitations on the scope of the invention, since modifications and optimizations may be made by those skilled in the art based on the foregoing teachings. The experimental procedure, in which specific conditions are not noted in the examples below, is generally followed by conventional conditions.
Example 1: cs (cells) 2 LiLa 0.98 Ce 0.01 Sm 0.01 Br 6 Spontaneous nucleation crucible-down growth of scintillation crystals:
(1) CsBr, liBr, laBr with a purity of 99.99% was placed in a glove box under nitrogen atmosphere 3 、CeBr 3 And SmBr 2 Powder according to CsBr, liBr and LaBr 3 :CeBr 3 :SmBr 2 The stoichiometric ratio of =2:1:0.98:0.01:0.01 was matched, and CsBr 9.5601g, liBr 1.9507g, laBr were weighed out 3 8.3343g、CeBr 3 0.0853g and SmBr 2 0.0697g, mixing well;
(2) Filling raw material powder into a spontaneous nucleation quartz crucible, vacuumizing the crucible, utilizing oxyhydrogen flame gun flame to enable a quartz column positioned at a bulge of a narrow wall of a mouth of the crucible to be mutually fused with an inner wall, achieving a sealing effect, placing the quartz column into a ceramic downpipe, placing the downpipe on a downpipe mechanism, enabling the bottom of the crucible to rise to the upper edge position of a temperature gradient zone in a descending furnace, and then starting to rise temperature;
(3) Heating the raw materials to a molten state, and preserving heat for more than 8 hours;
(4) Lowering the quartz crucible by a lowering mechanism at a speed of 0.1 mm/hr;
(5) After the crucible was lowered to a preset distance, the temperature was slowly lowered to room temperature, and then taken out and transferred into a glove box. Breaking the crucible, taking out the crystal, cutting, grinding and polishing to obtain a wafer sample.
Example 2: cs (cells) 2 LiLa 0.97 Ce 0.02 Sm 0.01 Br 6 Spontaneous nucleation crucible-down growth of scintillation crystals:
(1) CsBr, liBr, laBr with a purity of 99.99% was placed in a glove box under nitrogen atmosphere 3 、CeBr 3 And SmBr 2 Powder according to CsBr, liBr and LaBr 3 :CeBr 3 :SmBr 2 The stoichiometric ratio of =2:1:0.97:0.02:0.01 was matched, and CsBr 9.5600g, liBr 1.9506g, laBr were weighed out 3 8.2491g、CeBr 3 0.1706g and SmBr 2 0.0697g, mixing well;
(2) Filling raw material powder into a spontaneous nucleation quartz crucible, vacuumizing the crucible, utilizing oxyhydrogen flame gun flame to enable a quartz column positioned at a bulge of a narrow wall of a mouth of the crucible to be mutually fused with an inner wall, achieving a sealing effect, placing the quartz column into a ceramic downpipe, placing the downpipe on a downpipe mechanism, enabling the bottom of the crucible to rise to the upper edge position of a temperature gradient zone in a descending furnace, and then starting to rise temperature;
(3) Heating the raw materials to a molten state, and preserving heat for more than 8 hours;
(4) Lowering the quartz crucible by a lowering mechanism at a speed of 0.2 mm/hr;
(5) After the crucible was lowered to a preset distance, the temperature was slowly lowered to room temperature, and then taken out and transferred into a glove box. Breaking the crucible, taking out the crystal, cutting, grinding and polishing to obtain a wafer sample.
The quality of the grown crystals is better (see figure 1). Excitation of the sample at 280nm with a light sourceThe emission center is 827nm, belonging to Sm 2+ 4f-5d (see fig. 2). The emission spectrum under the excitation of X-ray shows that the emission center is 775nm, belonging to Sm 2+ The emission intensity of which changes with a law similar to that of fluorescence spectrum (see fig. 3).
Example 3: cs (cells) 2 LiLa 0.95 Ce 0.02 Sm 0.03 Br 6 Spontaneous nucleation crucible-down growth of scintillation crystals:
(1) CsBr, liBr, laBr with a purity of 99.99% was placed in a glove box under nitrogen atmosphere 3 、CeBr 3 And SmBr 2 Powder according to CsBr, liBr and LaBr 3 :CeBr 3 :SmBr 2 The stoichiometric ratio of =2:1:0.95:0.02:0.03 was matched, and CsBr 9.5747g, liBr 1.9536g, laBr were weighed out 3 8.0914g、CeBr 3 0.1709g and SmBr 2 0.2094g, mixing well;
(2) Filling raw material powder into a spontaneous nucleation quartz crucible, vacuumizing the crucible, utilizing oxyhydrogen flame gun flame to enable a quartz column positioned at a bulge of a narrow wall of a mouth of the crucible to be mutually fused with an inner wall, achieving a sealing effect, placing the quartz column into a ceramic downpipe, placing the downpipe on a downpipe mechanism, enabling the bottom of the crucible to rise to the upper edge position of a temperature gradient zone in a descending furnace, and then starting to rise temperature;
(3) Heating the raw materials to a molten state, and preserving heat for more than 8 hours;
(4) Lowering the quartz crucible by a lowering mechanism at a speed of 0.2 mm/hr;
(5) After the crucible was lowered to a preset distance, the temperature was slowly lowered to room temperature, and then taken out and transferred into a glove box. Breaking the crucible, taking out the crystal, cutting, grinding and polishing to obtain a wafer sample.
The quality of the grown crystals is better (see figure 1). Under the excitation of 280nm light source, the emission center of the sample is 827nm, belonging to Sm 2+ Is shown (see fig. 2). The emission spectrum under the excitation of X-ray shows that the emission center is 775nm, belonging to Sm 2+ Luminescence, the emission intensity of which varies with a law similar to that of fluorescence spectrum (see fig. 3).
Example 4: cs (cells) 2 LiLa 0.93 Ce 0.02 Sm 0.05 Br 6 Spontaneous nucleation crucible-down growth of scintillation crystals:
(1) CsBr, liBr, laBr with a purity of 99.99% was placed in a glove box under nitrogen atmosphere 3 、CeBr 3 And SmBr 2 Powder according to CsBr, liBr and LaBr 3 :CeBr 3 :SmBr 2 Stoichiometric ratio of =2:1:0.93:0.02:0.05, and weighing CsBr 9.5894g, liBr 1.9567g, laBr 3 7.9333g、CeBr 3 0.1711g and SmBr 2 0.3495g, mixing well;
(2) Filling raw material powder into a spontaneous nucleation quartz crucible, vacuumizing the crucible, utilizing oxyhydrogen flame gun flame to enable a quartz column positioned at a bulge of a narrow wall of a mouth of the crucible to be mutually fused with an inner wall, achieving a sealing effect, placing the quartz column into a ceramic downpipe, placing the downpipe on a downpipe mechanism, enabling the bottom of the crucible to rise to the upper edge position of a temperature gradient zone in a descending furnace, and then starting to rise temperature;
(3) Heating the raw materials to a molten state, and preserving heat for more than 8 hours;
(4) Lowering the quartz crucible by a lowering mechanism at a speed of 0.2 mm/hr;
(5) After the crucible was lowered to a preset distance, the temperature was slowly lowered to room temperature, and then taken out and transferred into a glove box. Breaking the crucible, taking out the crystal, cutting, grinding and polishing to obtain a wafer sample.
The quality of the grown crystals is better (see figure 1). Under the excitation of 280nm light source, the emission center of the sample is 827nm, the range is 800-850nm, and the sample belongs to Sm 2+ Luminescence, the emission intensity of which is significantly improved compared to the crystals of the other two components (see fig. 2). The emission center under the excitation of X-ray is 775nm, the range is 650-900nm, and the X-ray belongs to Sm 2+ Luminescence, the emission intensity of which varies with a law similar to that of fluorescence spectrum (see fig. 3).
Example 5: cs (cells) 2 LiLa 0.96 Ce 0.03 Sm 0.01 Br 6 Spontaneous nucleation crucible-down growth of scintillation crystals:
(1) In a glove box under nitrogen atmosphere, the mixture was purifiedCsBr, liBr, laBr having a degree of 99.99% 3 、CeBr 3 And SmBr 2 Powder according to CsBr, liBr and LaBr 3 :CeBr 3 :SmBr 2 The stoichiometric ratio of =2:1:0.96:0.03:0.01 was matched, and CsBr 9.5598g, liBr 1.9506g, laBr were weighed out 3 8.1639g、CeBr 3 0.2559g and SmBr 2 0.0697g, mixing well;
(2) Filling raw material powder into a quartz crucible, vacuumizing the crucible, utilizing oxyhydrogen flame gun flame to enable a quartz column positioned at a bulge of a narrow wall of a mouth of the crucible to be mutually fused with an inner wall, achieving a sealing effect, placing the quartz column into a ceramic downpipe, placing the downpipe on a downpipe mechanism, enabling the bottom of the crucible to rise to the upper edge position of a temperature gradient zone in a descending furnace, and then starting to rise;
(3) Heating the raw materials to a molten state, and preserving heat for more than 8 hours;
(4) Lowering the quartz crucible by a lowering mechanism at a speed of 0.3 mm/hr;
(5) After the crucible was lowered to a preset distance, the temperature was slowly lowered to room temperature, and then taken out and transferred into a glove box. Breaking the crucible, taking out the crystal, cutting, grinding and polishing to obtain a wafer sample.
Example 6: cs (cells) 2 LiLa 0.91 Ce 0.02 Sm 0.07 Br 6 Spontaneous nucleation crucible-down growth of scintillation crystals:
(1) CsBr, liBr, laBr with a purity of 99.99% was placed in a glove box under nitrogen atmosphere 3 、CeBr 3 And SmBr 2 Powder according to CsBr, liBr and LaBr 3 :CeBr 3 :SmBr 2 The stoichiometric ratio of =2:1:0.91:0.02:0.07 was calculated and CsBr 9.6042g, liBr 1.9597g and LaBr were weighed out 3 7.7747g、CeBr 3 0.1714g and SmBr 2 0.4900g, mixing well;
(2) Filling raw material powder into a spontaneous nucleation quartz crucible, vacuumizing the crucible, utilizing oxyhydrogen flame gun flame to enable a quartz column positioned at a bulge of a narrow wall of a mouth of the crucible to be mutually fused with an inner wall, achieving a sealing effect, placing the quartz column into a ceramic downpipe, placing the downpipe on a downpipe mechanism, enabling the bottom of the crucible to rise to the upper edge position of a temperature gradient zone in a descending furnace, and then starting to rise temperature;
(3) Heating the raw materials to a molten state, and preserving heat for more than 8 hours;
(4) Lowering the quartz crucible by a lowering mechanism at a speed of 0.2 mm/hr;
(5) After the crucible was lowered to a preset distance, the temperature was slowly lowered to room temperature, and then taken out and transferred into a glove box. Breaking the crucible, taking out the crystal, cutting, grinding and polishing to obtain a wafer sample.
Example 7: cs (cells) 2 LiLa 0.97 Sm 0.03 Br 6 Spontaneous nucleation crucible-down growth of scintillation crystals:
(1) CsBr, liBr, laBr with a purity of 99.99% was placed in a glove box under nitrogen atmosphere 3 And SmBr 2 Powder according to CsBr, liBr and LaBr 3 :SmBr 2 The stoichiometric ratio of =2:1:0.97:0.03 was matched, and CsBr 9.5749g, libr1.9537g, laBr were weighed out 3 8.2620g and SmBr 2 0.2094g, mixing well;
(2) Filling raw material powder into a spontaneous nucleation quartz crucible, vacuumizing the crucible, utilizing oxyhydrogen flame gun flame to enable a quartz column positioned at a bulge of a narrow wall of a mouth of the crucible to be mutually fused with an inner wall, achieving a sealing effect, placing the quartz column into a ceramic downpipe, placing the downpipe on a downpipe mechanism, enabling the bottom of the crucible to rise to the upper edge position of a temperature gradient zone in a descending furnace, and then starting to rise temperature;
(3) Heating the raw materials to a molten state, and preserving heat for more than 8 hours;
(4) Lowering the quartz crucible by a lowering mechanism at a speed of 1 mm/hr;
(5) After the crucible was lowered to a preset distance, the temperature was slowly lowered to room temperature, and then taken out and transferred into a glove box. Breaking the crucible, taking out the crystal, cutting, grinding and polishing to obtain a wafer sample.
Example 8: cs (cells) 2 LiLa 0.94 Ce 0.05 Sm 0.01 Br 6 Spontaneous nucleation crucible-down growth of scintillation crystals:
(1) In nitrogen atmosphereCsBr, liBr, laBr with 99.99% purity was put in a glove box 3 、CeBr 3 And SmBr 2 Powder according to CsBr, liBr and LaBr 3 :CeBr 3 :SmBr 2 The stoichiometric ratio of =2:1:0.94:0.05:0.01 was matched, and CsBr 9.5596g, liBr 1.9506g, laBr were weighed out 3 7.9936g、CeBr 3 0.4265g and SmBr 2 0.0697g, mixing well;
(2) Filling raw material powder into a spontaneous nucleation quartz crucible, vacuumizing the crucible, utilizing oxyhydrogen flame gun flame to enable a quartz column positioned at a bulge of a narrow wall of a mouth of the crucible to be mutually fused with an inner wall, achieving a sealing effect, placing the quartz column into a ceramic downpipe, placing the downpipe on a downpipe mechanism, enabling the bottom of the crucible to rise to the upper edge position of a temperature gradient zone in a descending furnace, and then starting to rise temperature;
(3) Heating the raw materials to a molten state, and preserving heat for more than 8 hours;
(4) Lowering the quartz crucible by a lowering mechanism at a speed of 0.5 mm/hr;
(5) After the crucible was lowered to a preset distance, the temperature was slowly lowered to room temperature, and then taken out and transferred into a glove box. Breaking the crucible, taking out the crystal, cutting, grinding and polishing to obtain a wafer sample.
Example 9: cs (cells) 2 LiLa 0.9 Ce 0.1 Br 6 Spontaneous nucleation crucible-down growth of scintillation crystals:
(1) CsBr, liBr and CeBr with a purity of 99.99% were purified in a glove box under nitrogen atmosphere 3 Powder according to CsBr, liBr and LaBr 3 :CeBr 3 The stoichiometric ratio of =2:1:0.9:0.1 was matched, and CsBr 9.5413g, liBr 1.9468g, laBr were weighed out 3 0.8488g and CeBr 3 7.6631g, mixing well;
(2) Filling raw material powder into a spontaneous nucleation quartz crucible, vacuumizing the crucible, utilizing oxyhydrogen flame gun flame to enable a quartz column positioned at a bulge of a narrow wall of a mouth of the crucible to be mutually fused with an inner wall, achieving a sealing effect, placing the quartz column into a ceramic downpipe, placing the downpipe on a downpipe mechanism, enabling the bottom of the crucible to rise to the upper edge position of a temperature gradient zone in a descending furnace, and then starting to rise temperature;
(3) Heating the raw materials to a molten state, and preserving heat for more than 8 hours;
(4) Lowering the quartz crucible by a lowering mechanism at a speed of 1 mm/hr;
(5) After the crucible was lowered to a preset distance, the temperature was slowly lowered to room temperature, and then taken out and transferred into a glove box. Breaking the crucible, taking out the crystal, cutting, grinding and polishing to obtain a wafer sample.
Claims (6)
1. Ce (cerium) 3+ 、Sm 2+ Co-doped multicomponent near infrared halide scintillation crystals having the formula Cs 2 LiLa 1-x-y Ce x Sm y Br 6 。
2. Ce according to claim 1 3+ 、Sm 2+ The co-doped multicomponent near infrared halide scintillation crystal is characterized in that the value range of x is more than 0 and less than or equal to 0.1, and the value range of y is more than 0 and less than or equal to 0.05.
3. Ce according to any one of claims 1-2 3+ 、Sm 2+ Co-doped multicomponent near infrared halide scintillation crystal Cs 2 LiLa 1-x-y Ce x Sm y Br 6 The crystal can emit broadband near infrared light between 650 nm and 900nm under the excitation of high-energy rays or high-energy particles.
4. A Ce according to any one of claims 1 to 3 3+ 、Sm 2+ A method of preparing a co-doped multicomponent near infrared halide scintillation crystal comprising: will CsBr, liBr, laBr 3 、CeBr 3 And SmBr 2 Mixing the powder according to a certain proportion, filling the mixture into a spontaneous nucleation quartz crucible, vacuum sealing, heating and melting the powder, and performing crystal growth to obtain the crystal.
5. Ce according to claim 4 3+ 、Sm 2+ A method for preparing a co-doped multicomponent near infrared halide scintillation crystal is characterized in that CsBr, liBr, laBr is obtained 3 、CeBr 3 And SmBr 2 The powder is prepared by mixing x and y according to the molar ratio of 2:1 (1-x-y), wherein x is more than 0 and less than or equal to 0.1, and y is more than 0 and less than or equal to 0.05; growing the Cs by a crucible descent method using the raw material powder 2 LiLa 1-x-y Ce x Sm y Br 6 A halide scintillation crystal of elpasolite structure.
6. Ce according to any one of claims 1-2 3+ 、Sm 2+ The application of the co-doped multicomponent near infrared halide scintillation crystal is characterized in that the co-doped multicomponent near infrared halide scintillation crystal has good application in the fields of near infrared and high-energy ray detection and imaging.
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