CN108531988A - A kind of preparation method of rare earth halide scintillation crystal and application - Google Patents
A kind of preparation method of rare earth halide scintillation crystal and application Download PDFInfo
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- CN108531988A CN108531988A CN201810436170.2A CN201810436170A CN108531988A CN 108531988 A CN108531988 A CN 108531988A CN 201810436170 A CN201810436170 A CN 201810436170A CN 108531988 A CN108531988 A CN 108531988A
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- C—CHEMISTRY; METALLURGY
- C30—CRYSTAL GROWTH
- C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
- C30B29/00—Single crystals or homogeneous polycrystalline material with defined structure characterised by the material or by their shape
- C30B29/10—Inorganic compounds or compositions
- C30B29/12—Halides
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- C—CHEMISTRY; METALLURGY
- C30—CRYSTAL GROWTH
- C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
- C30B11/00—Single-crystal growth by normal freezing or freezing under temperature gradient, e.g. Bridgman-Stockbarger method
- C30B11/02—Single-crystal growth by normal freezing or freezing under temperature gradient, e.g. Bridgman-Stockbarger method without using solvents
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Abstract
The invention discloses a kind of preparation method of rare earth halide scintillation crystal and application, the first constitutional chemistry formula Cs according to rare earth halide scintillation crystal to be prepared in crystal growth of the preparation method2Li1+yLa1‑xCexCl6Weigh each raw material；Then it in the environment full of inert gas, by each raw material grind into powder, and is uniformly mixed；Then obtained mixed-powder raw material will be uniformly mixed to be placed in silica crucible, be evacuated and hermetically sealed；Rare earth halide scintillation crystal is prepared using Bridgman-Stockbarger method again；Advantage is that the scintillation crystal being prepared is the CLLC scintillation crystals of High-quality transparent, and photoyield is high, energy resolution is good, neutron gamma examination performance is good.
Description
Technical field
The present invention relates to a kind of technologies of preparing of crystalline material, more particularly, to a kind of system of rare earth halide scintillation crystal
Preparation Method and application.
Background technology
In recent years, being widely used with radioactive material can detect and effectively screen out thermal neutron and gamma simultaneously
The double reading detectors of thermal neutron-gamma of ray prevent nuclear proliferation, nuclear leakage, safety check and nuclear radiation environment protection etc.
Using increasingly important.It is generally comprised there are two types of detector in the present double reading detectors of widely used thermal neutron-gamma,
One is thermal-neutron detectors, such as He-3 flues；Another is gamma-ray detector, such as NaI:Tl crystal counters；
Two kinds of detectors only work and could detect thermal neutron and gamma ray simultaneously together.Thermal neutron detection mainly utilizes neutron
(such as with the specific isotope in thermal neutron detection material3He、6Li and10B it) reacts, releases α particles, and then in indirect detection
Son；Gamma ray detection is mainly shone using gamma ray activation scintillation crystal, to be detected by energy spectrometer.Energy
There are many enough types to detect the scintillation crystal of gamma ray and the main contents of scintillation crystal research；And thermal neutron is visited
It surveys due to needing to contain in thermal neutron detection material3He、6Li or10The specific isotopes such as B, therefore the kind of thermal neutron detection material
Class is many less, and develops slowly.Traditional thermal-neutron detector is3He proportional counter tubes, but recent years,3He resources are close
Exhaustion, available resources have been unable to meet needs.
There are many type of the double reading detectors of thermal neutron-gamma, such as：Thermal neutron-gamma based on inorganic scintillator is double to read
Go out detector, because simple in structure, detection efficient is high, energy and time resolution performance are good, it has also become the main side of future development
To.Currently, in inorganic thermal neutron detection scintillator, practical inorganic thermal neutron detection scintillator mainly has6LiI is brilliant
Body,6Li glass and6LiF/ZnS composite materials,6The die-away time of LiI crystal is long,6The light output of Li glass is low and energy resolution
Rate is low,6The detection efficient of LiF/ZnS composite materials is low and die-away time is long, these inorganic thermal neutron detection scintillators are all difficult
For in the double reading detectors of thermal neutron-gamma ray.Other than these above-mentioned inorganic thermal neutron detection scintillators, in the past few years
Have developed some novel inorganic thermal neutron detection scintillation crystals, wherein most noticeable to surely belong to Dutch Deft technologies big
Take the lead in studying, the Ce that RMD companies of the U.S. and company of French Saint-Gobain develop in succession:Cs2LiYCl6(CLYC)、Ce:
Cs2LiLaCl6(CLLC)、Ce:Cs2LiLaBr6(CLLB) and Ce:Cs2LiYBr6(CLYB) etc. a series of that there is elpasolite
(Elpasolite) the novel inorganic thermal neutron detection scintillation crystal with very superior scintillation properties of structure feature.
In view of the inorganic thermal neutron detection scintillation crystal with elpasolite structure feature with superior thermal neutron and gal
Horse X-ray detection X performance, the series scintillation crystal one is it has been observed that will attract wide public concern.CLYC scintillation crystals are due in gal
Core-the valence (core-valence, CVL) that is exceedingly fast under the excitation of horse ray there is 1ns or so shines, and under thermal neutron excitation not
There are CVL to shine, therefore has excellent neutron/gamma ray pulse shape (PSD) discrimination capabilities, is current inorganic thermal neutron
Detect scintillation crystal research and market-oriented most popular scintillation crystal.But for from scintillation properties, CLLC scintillation crystals and
CLYC scintillation crystals are the same, and all only there is CVL to shine under gamma ray excitation, equally have PSD discrimination capabilities.Meanwhile
CLLC scintillation crystals have higher light output and higher energy resolution, energy coincidence compared to CLYC scintillation crystals
Property is even better than LaBr3:Ce crystal especially also has good consistency under the excitation of low-energy gamma ray.It is dodged with CLYC
Bright crystal phase ratio, CLLC scintillation crystals have the advantages that light output is high, energy resolution is high；Compared with CLLB scintillation crystals,
CLLC scintillation crystals have the advantages that neutron-gamma discrimination capabilities are strong.Therefore, CLLC scintillation crystals be a kind of comprehensive performance more
Excellent neutron-gamma is double to read scintillation crystal.
CLYC scintillation crystals are congruent melting crystal, are adapted for use with Bridgman-Stockbarge method for growing, therefore CLYC scintillation crystals
It is easier to go out large-size crystals using Bridgman-Stockbarge method for growing, has grown a diameter of 3 English using Bridgman-Stockbarger method at present
Very little high quality crystal.And CLLC scintillation crystals mainly contain CsCl, LiCl and LaCl due to component3, using common crucible
Descent method matches raw material using stoichiometric ratio, easily occurs component deviation in growth course, lead to Cs occur2LiLaCl6
And CsLaCl6Mixture, therefore can not yet grow the scintillation crystal of High-quality transparent at present.Therefore, research passes through life
The adjustment of formula of long raw material grows High-quality transparent and possesses the flicker of higher photoyield and more preferably energy resolution
Crystal is very valuable.
Invention content
Technical problem to be solved by the invention is to provide a kind of preparation method of rare earth halide scintillation crystal and application,
The scintillation crystal that the preparation method is prepared is the CLLC scintillation crystals of High-quality transparent, and photoyield is high, energy resolution
It is good that good, neutron-gamma screens performance.
Technical solution is used by the present invention solves above-mentioned technical problem：A kind of preparation of rare earth halide scintillation crystal
Method, it is characterised in that the preparation method prepares rare earth halide scintillation crystal using Bridgman-Stockbarger method, which includes
Following steps：
Step 1：The constitutional chemistry formula of rare earth halide scintillation crystal to be prepared is Cs2LiLa1-xCexCl6, according to waiting for
Constitutional chemistry formula Cs of the rare earth halide scintillation crystal of preparation in crystal growth2Li1+yLa1-xCexCl6Each raw material is weighed, is made
Inhibit the Cs occurred in crystal growing process with excessive LiCl3LaCl6Impurity phase, to grow the CLLC of High-quality transparent
Scintillation crystal, wherein the value range of x is 0.0001≤x≤0.1, and the value range of y is 0.01≤y≤0.4；
Step 2：In the environment full of inert gas, by each raw material grind into powder, all powder for then will being ground into
Powder stock is uniformly mixed；
Step 3：Obtained mixed-powder raw material will be uniformly mixed to be placed in silica crucible；Then silica crucible is pumped into
Vacuum state；Then sealing is carried out to realize excellent sealing to the silica crucible of vacuum state；
Step 4：The silica crucible being sealed is put into the crucible placed vertically vertically to decline on the centre position of stove；So
Afterwards to crucible decline stove heat up, make temperature be more than rare earth halide scintillation crystal to be prepared 50 DEG C of fusion temperature extremely
100 DEG C of ranges, until mixed-powder raw material all melts, and material uniformly obtains melt；Then decline stove to crucible to drop
Temperature makes the temperature of the bottom of silica crucible be down to 450~480 DEG C, then makes silica crucible with the decrease speed of 0.01~2.0mm/h
Decline in crucible declines stove, until melt is frozen into solid；Crucible is set to decline stove with the rate of temperature fall of 10~50 DEG C/h later
Cooling has so far grown rare earth halide scintillation crystal until being down to room temperature in silica crucible；Finally in dry environment,
The rare earth halide scintillation crystal prepared is taken out from silica crucible.Here, rare earth halide scintillation crystal to be prepared
Fusion temperature in crystal growth is because of dispensing component Cs2Li1+yLa1-xCexCl6Difference (difference of x, y value) without
Together, in the range of 450~470 DEG C, but the component of transparent crystal does not change due to the change of LiCl contents in composition of raw materials, still
For Cs2LiLa1-xCexCl6, present scintillation properties remain as Cs2LiLa1-xCexCl6The typical Flash characteristic of scintillation crystal.
In the step one, raw material has CsCl, LiCl, LaCl3And CeCl3.Wherein, LiCl raw materials can both use day
The LiCl of right abundance can also use enrichment6Li isotopes6LiCl；The purity of all raw materials is 99.99% or more；It is all
Raw material is super dry anhydrous raw material, and water content is less than 10ppm.
In the step two, the environment full of inert gas is the glove box full of inert gas.Here, inertia
Gas is high pure nitrogen or argon gas, the H in glove box2O and O2Content is below 1ppm.
In the step three, using molecular pump by silica crucible vacuum state；Using acetylene flame to vacuum state
Silica crucible carry out sealing.
A kind of rare earth halide scintillation crystal that the preparation method of above-mentioned rare earth halide scintillation crystal is prepared
Using, it is characterised in that the rare earth halide scintillation crystal is answered neutron detection, gamma ray detection or flash detection field
With.
Compared with the prior art, the advantages of the present invention are as follows：
1) in the constitutional chemistry formula Cs of the rare earth halide scintillation crystal2LiLa1-xCexCl6On the basis of, in crystal growth
The constitutional chemistry formula Cs of the excessive a part of LiCl of Shi Caiyong2Li1+yLa1-xCexCl6It weighs each raw material and carries out crystal growth, used
The LiCl of amount inhibits the Cs occurred in crystal growing process3LaCl6Impurity phase, the CLLC so as to grow High-quality transparent dodge
Bright crystal.
2) play the role of the cerium ion of the centre of luminescence in the rare earth halide scintillation crystal in the form of+trivalent to exist, account for
La is taken3+Ion site.
3) the rare earth halide scintillation crystal and Ce:Cs2LiYCl6(CLYC) it compares, due to containing La elements, has
Higher photoyield, more preferably energy resolution, more superior neutron-gamma discrimination capabilities.
Description of the drawings
Fig. 1 is to utilize the constitutional chemistry formula Cs in the method for the present invention2Li1+yLa1-xCexCl6(x=0.005, y=0.01,
0.10,0.20 and 0.40) it is formulated the rare earth halide scintillation crystal (Cs that grows2LiLa1-xCexCl6) wave under excitation of X-rays
The long Ce between 350~450nm3+Ionoluminescence schematic diagram；
Fig. 2 is to utilize the constitutional chemistry formula Cs in the method for the present invention2Li1+yLa1-xCexCl6(x=0.005, y=0.01,
0.10,0.20 and 0.40) it is formulated the rare earth halide scintillation crystal (Cs that grows2LiLa1-xCexCl6) wave under excitation of X-rays
The luminous schematic diagram of the long core valence between 250~320nm.
Specific implementation mode
Below in conjunction with attached drawing embodiment, present invention is further described in detail.
Embodiment one：
A kind of preparation method for rare earth halide scintillation crystal that the present embodiment proposes, the preparation method are declined using crucible
Method prepares rare earth halide scintillation crystal, which includes the following steps：
Step 1：The constitutional chemistry formula of rare earth halide scintillation crystal to be prepared is Cs2LiLa0.995Ce0.005Cl6, press
According to the constitutional chemistry formula Cs of rare earth halide scintillation crystal to be prepared in crystal growth2Li1.01La0.995Ce0.005Cl6It weighs
Each raw material.
In the step one, raw material has CsCl, LiCl, LaCl3And CeCl3.Wherein, LiCl raw materials can both use day
The LiCl of right abundance can also use enrichment6Li isotopes6LiCl；The purity of all raw materials is 99.99% or more；It is all
Raw material is super dry anhydrous raw material, and water content is less than 10ppm.
Here, in the constitutional chemistry formula Cs of the rare earth halide scintillation crystal2Li La0.995Ce0.005Cl6On the basis of,
Using the constitutional chemistry formula Cs of excessive a part of LiCl when crystal growth2Li1.01La0.995Ce0.005Cl6It weighs each raw material and carries out crystalline substance
Body is grown, and inhibits the Cs occurred in crystal growing process using excessive LiCl3LaCl6Impurity phase, so as to grow high quality
Transparent CLLC scintillation crystals；Play the role of the cerium ion of the centre of luminescence in the rare earth halide scintillation crystal in the form of+trivalent
In the presence of having occupied La3+Ion site.
Step 2：In the environment full of inert gas, by each raw material grind into powder, all powder for then will being ground into
Powder stock is uniformly mixed.
In the step two, the environment full of inert gas is the glove box full of inert gas.Here, inertia
Gas is high pure nitrogen or argon gas, the H in glove box2O and O2Content is below 1ppm.
Step 3：Obtained mixed-powder raw material will be uniformly mixed to be placed in silica crucible；Then silica crucible is pumped into
Vacuum state；Then sealing is carried out to realize excellent sealing to the silica crucible of vacuum state.
In the step three, using molecular pump by silica crucible vacuum state；Using acetylene flame to vacuum state
Silica crucible carry out sealing.
Step 4：The silica crucible being sealed is put into the crucible placed vertically vertically to decline on the centre position of stove；So
Afterwards to crucible decline stove heat up, make temperature be more than rare earth halide scintillation crystal to be prepared fusion temperature (about 460~
470 DEG C) 50 DEG C to 100 DEG C of ranges, so that temperature is reached 510~570 DEG C or so herein, until mixed-powder raw material all melts,
And material uniformly obtains melt；Then to crucible decline stove cool down, make the temperature of the bottom of silica crucible be down to 480 DEG C it is attached
Closely, then with the decrease speed of 0.6mm/h make silica crucible crucible decline stove in decline, crystal take the lead in capillary bottom crystallization,
Nucleation, by growth in about 20~40 days, until melt is frozen into solid；Crucible is set to decline with the rate of temperature fall of 20 DEG C/h later
Stove cools down, until being down to room temperature, rare earth halide scintillation crystal has so far been grown in silica crucible；Finally it is less than in water content
In the dry environment of 1000ppm, the rare earth halide scintillation crystal prepared is taken out from silica crucible, can will subsequently be taken out
Rare earth halide scintillation crystal be processed.
A kind of application of above-mentioned rare earth halide scintillation crystal, the rare earth halide scintillation crystal can be applied to neutron spy
Survey, gamma ray detection or flash detection field.
Embodiment two：
A kind of preparation method for rare earth halide scintillation crystal that the present embodiment proposes, the preparation method are declined using crucible
Method prepares rare earth halide scintillation crystal, which includes the following steps：
Step 1：The constitutional chemistry formula of rare earth halide scintillation crystal to be prepared is Cs2LiLa0.995Ce0.005Cl6, press
According to the constitutional chemistry formula Cs of rare earth halide scintillation crystal to be prepared in crystal growth2Li1.10La0.995Ce0.005Cl6It weighs
Each raw material.
In the step one, raw material has CsCl, LiCl, LaCl3And CeCl3.Wherein, LiCl raw materials can both use day
The LiCl of right abundance can also use enrichment6Li isotopes6LiCl；The purity of all raw materials is 99.99% or more；It is all
Raw material is super dry anhydrous raw material, and water content is less than 10ppm.
Here, in the constitutional chemistry formula Cs of the rare earth halide scintillation crystal2Li La0.995Ce0.005Cl6On the basis of,
Using the constitutional chemistry formula Cs of excessive a part of LiCl when crystal growth2Li1.10La0.995Ce0.005Cl6It weighs each raw material and carries out crystalline substance
Body is grown, and inhibits the Cs occurred in crystal growing process using excessive LiCl3LaCl6Impurity phase, so as to grow high quality
Transparent CLLC scintillation crystals；Play the role of the cerium ion of the centre of luminescence in the rare earth halide scintillation crystal in the form of+trivalent
In the presence of having occupied La3+Ion site.
Step 2：In the environment full of inert gas, by each raw material grind into powder, all powder for then will being ground into
Powder stock is uniformly mixed.
In the step two, the environment full of inert gas is the glove box full of inert gas.Here, inertia
Gas is high pure nitrogen or argon gas, the H in glove box2O and O2Content is below 1ppm.
Step 3：Obtained mixed-powder raw material will be uniformly mixed to be placed in silica crucible；Then silica crucible is pumped into
Vacuum state；Then sealing is carried out to realize excellent sealing to the silica crucible of vacuum state.
In the step three, using molecular pump by silica crucible vacuum state；Using acetylene flame to vacuum state
Silica crucible carry out sealing.
Step 4：The silica crucible being sealed is put into the crucible placed vertically vertically to decline on the centre position of stove；So
Afterwards to crucible decline stove heat up, make temperature be more than rare earth halide scintillation crystal to be prepared fusion temperature (about 450~
460 DEG C) 50 DEG C to 100 DEG C of ranges, so that temperature is reached 500~560 DEG C or so herein, until mixed-powder raw material all melts,
And material uniformly obtains melt；Then to crucible decline stove cool down, make the temperature of the bottom of silica crucible be down to 470 DEG C it is attached
Closely, then with the decrease speed of 0.4mm/h make silica crucible crucible decline stove in decline, crystal take the lead in capillary bottom crystallization,
Nucleation, by growth in about 20~40 days, until melt is frozen into solid；Crucible is set to decline with the rate of temperature fall of 20 DEG C/h later
Stove cools down, until being down to room temperature, rare earth halide scintillation crystal has so far been grown in silica crucible；Finally it is less than in water content
In the dry environment of 1000ppm, the rare earth halide scintillation crystal prepared is taken out from silica crucible, can will subsequently be taken out
Rare earth halide scintillation crystal be processed.
A kind of application of above-mentioned rare earth halide scintillation crystal, the rare earth halide scintillation crystal can be applied to neutron spy
Survey, gamma ray detection or flash detection field.
Embodiment three：
A kind of preparation method for rare earth halide scintillation crystal that the present embodiment proposes, the preparation method are declined using crucible
Method prepares rare earth halide scintillation crystal, which includes the following steps：
Step 1：The constitutional chemistry formula of rare earth halide scintillation crystal to be prepared is Cs2LiLa0.995Ce0.005Cl6, press
According to the constitutional chemistry formula Cs of rare earth halide scintillation crystal to be prepared in crystal growth2Li1.20La0.995Ce0.005Cl6It weighs
Each raw material.
In the step one, raw material has CsCl, LiCl, LaCl3And CeCl3.Wherein, LiCl raw materials can both use day
The LiCl of right abundance can also use enrichment6Li isotopes6LiCl；The purity of all raw materials is 99.99% or more；It is all
Raw material is super dry anhydrous raw material, and water content is less than 10ppm.
Here, in the constitutional chemistry formula Cs of the rare earth halide scintillation crystal2Li La0.995Ce0.005Cl6On the basis of,
Using the constitutional chemistry formula Cs of excessive a part of LiCl when crystal growth2Li1.20La0.995Ce0.005Cl6It weighs each raw material and carries out crystalline substance
Body is grown, and inhibits the Cs occurred in crystal growing process using excessive LiCl3LaCl6Impurity phase, so as to grow high quality
Transparent CLLC scintillation crystals；Play the role of the cerium ion of the centre of luminescence in the rare earth halide scintillation crystal in the form of+trivalent
In the presence of having occupied La3+Ion site.
Step 2：In the environment full of inert gas, by each raw material grind into powder, all powder for then will being ground into
Powder stock is uniformly mixed.
In the step two, the environment full of inert gas is the glove box full of inert gas.Here, inertia
Gas is high pure nitrogen or argon gas, the H in glove box2O and O2Content is below 1ppm.
Step 3：Obtained mixed-powder raw material will be uniformly mixed to be placed in silica crucible；Then silica crucible is pumped into
Vacuum state；Then sealing is carried out to realize excellent sealing to the silica crucible of vacuum state.
In the step three, using molecular pump by silica crucible vacuum state；Using acetylene flame to vacuum state
Silica crucible carry out sealing.
Step 4：The silica crucible being sealed is put into the crucible placed vertically vertically to decline on the centre position of stove；So
Afterwards to crucible decline stove heat up, make temperature be more than rare earth halide scintillation crystal to be prepared fusion temperature (about 450~
460 DEG C) 50 DEG C to 100 DEG C of ranges, so that temperature is reached 500~560 DEG C or so herein, until mixed-powder raw material all melts,
And material uniformly obtains melt；Then to crucible decline stove cool down, make the temperature of the bottom of silica crucible be down to 470 DEG C it is attached
Closely, then with the decrease speed of 0.3mm/h make silica crucible crucible decline stove in decline, crystal take the lead in capillary bottom crystallization,
Nucleation, by growth in about 30~50 days, until melt is frozen into solid；Crucible is set to decline with the rate of temperature fall of 20 DEG C/h later
Stove cools down, until being down to room temperature, rare earth halide scintillation crystal has so far been grown in silica crucible；Finally it is less than in water content
In the dry environment of 1000ppm, the rare earth halide scintillation crystal prepared is taken out from silica crucible, can will subsequently be taken out
Rare earth halide scintillation crystal be processed.
A kind of application of above-mentioned rare earth halide scintillation crystal, the rare earth halide scintillation crystal can be applied to neutron spy
Survey, gamma ray detection or flash detection field.
Example IV：
A kind of preparation method for above-mentioned rare earth halide scintillation crystal that the present embodiment proposes, the preparation method use earthenware
Crucible descent method prepares rare earth halide scintillation crystal, which includes the following steps：
Step 1：The constitutional chemistry formula of rare earth halide scintillation crystal to be prepared is Cs2Li La0.995Ce0.005Cl6, press
According to the constitutional chemistry formula Cs of rare earth halide scintillation crystal to be prepared in crystal growth2Li1.40La0.995Ce0.005Cl6It weighs
Each raw material.
In the step one, raw material has CsCl, LiCl, LaCl3And CeCl3.Wherein, LiCl raw materials can both use day
The LiCl of right abundance can also use enrichment6Li isotopes6LiCl；The purity of all raw materials is 99.99% or more；It is all
Raw material is super dry anhydrous raw material, and water content is less than 10ppm.
Here, in the constitutional chemistry formula Cs of the rare earth halide scintillation crystal2Li La0.995Ce0.005Cl6On the basis of,
Using the constitutional chemistry formula Cs of excessive a part of LiCl when crystal growth2Li1.40La0.995Ce0.005Cl6It weighs each raw material and carries out crystalline substance
Body is grown, and inhibits the Cs occurred in crystal growing process using excessive LiCl3LaCl6Impurity phase, so as to grow high quality
Transparent CLLC scintillation crystals；Play the role of the cerium ion of the centre of luminescence in the rare earth halide scintillation crystal in the form of+trivalent
In the presence of having occupied La3+Ion site.
Step 2：In the environment full of inert gas, by each raw material grind into powder, all powder for then will being ground into
Powder stock is uniformly mixed.
In the step two, the environment full of inert gas is the glove box full of inert gas.Here, inertia
Gas is high pure nitrogen or argon gas, the H in glove box2O and O2Content is below 1ppm.
Step 3：Obtained mixed-powder raw material will be uniformly mixed to be placed in silica crucible；Then silica crucible is pumped into
Vacuum state；Then sealing is carried out to realize excellent sealing to the silica crucible of vacuum state.
In the step three, using molecular pump by silica crucible vacuum state；Using acetylene flame to vacuum state
Silica crucible carry out sealing.
Step 4：The silica crucible being sealed is put into the crucible placed vertically vertically to decline on the centre position of stove；So
Afterwards to crucible decline stove heat up, make temperature be more than rare earth halide scintillation crystal to be prepared fusion temperature (about 450~
460 DEG C) 50 DEG C to 100 DEG C of ranges, so that temperature is reached 500~560 DEG C or so herein, until mixed-powder raw material all melts,
And material uniformly obtains melt；Then to crucible decline stove cool down, make the temperature of the bottom of silica crucible be down to 470 DEG C it is attached
Closely, then with the decrease speed of 0.2mm/h make silica crucible crucible decline stove in decline, crystal take the lead in capillary bottom crystallization,
Nucleation, by growth in about 40~60 days, until melt is frozen into solid；Crucible is set to decline with the rate of temperature fall of 20 DEG C/h later
Stove cools down, until being down to room temperature, rare earth halide scintillation crystal has so far been grown in silica crucible；Finally it is less than in water content
In the dry environment of 1000ppm, the rare earth halide scintillation crystal prepared is taken out from silica crucible, can will subsequently be taken out
Rare earth halide scintillation crystal be processed.
A kind of application of above-mentioned rare earth halide scintillation crystal, the rare earth halide scintillation crystal can be applied to neutron spy
Survey, gamma ray detection or flash detection field.
Fig. 1, which gives, utilizes the constitutional chemistry formula Cs in the method for the present invention2Li1+yLa1-xCexCl6(x=0.005, y=
0.01,0.10,0.20 and 0.40) it is formulated the rare earth halide scintillation crystal (Cs that grows2LiLa1-xCexCl6) swash in X-ray
Give Ce of the wavelength between 350~450nm3+Ionoluminescence schematic diagram；Fig. 2, which gives, utilizes the composition in the method for the present invention
Chemical formula Cs2Li1+yLa1-xCexCl6(x=0.005, y=0.01,0.10,0.20 and 0.40) be formulated the rare earth halide that grows
Object scintillation crystal (Cs2LiLa1-xCexCl6) core valence of the wavelength between 250~320nm shines and illustrate under excitation of X-rays
Figure.It is respectively the flicker crystalline substance grown in 0.01,0.10,0.20 and 0.40 formula from being can be seen that in Fig. 1 and Fig. 2 from y values
There is Ce under excitation of X-rays in body3+Ionoluminescence and core valence shine, have good neutron-gamma discrimination performance,
Wherein from formula Cs2Li1.01La0.995Ce0.005Cl6The scintillation crystal grown shines most strong.
Claims (5)
1. a kind of preparation method of rare earth halide scintillation crystal, it is characterised in that the preparation method is prepared using Bridgman-Stockbarger method
Rare earth halide scintillation crystal, the preparation method include the following steps：
Step 1：The constitutional chemistry formula of rare earth halide scintillation crystal to be prepared is Cs2LiLa1-xCexCl6, according to be prepared
Constitutional chemistry formula Cs of the rare earth halide scintillation crystal in crystal growth2Li1+yLa1-xCexCl6Weigh each raw material, wherein x
Value range be 0.0001≤x≤0.1, the value range of y is 0.01≤y≤0.4；
Step 2：In the environment full of inert gas, by each raw material grind into powder, then by all powder being ground into original
Material is uniformly mixed；
Step 3：Obtained mixed-powder raw material will be uniformly mixed to be placed in silica crucible；Then silica crucible is evacuated
State；Then sealing is carried out to realize excellent sealing to the silica crucible of vacuum state；
Step 4：The silica crucible being sealed is put into the crucible placed vertically vertically to decline on the centre position of stove；Then right
Crucible declines stove and heats up, and it is more than 50 DEG C to 100 DEG C of the fusion temperature of rare earth halide scintillation crystal to be prepared to make temperature
Range, until mixed-powder raw material all melts, and material uniformly obtains melt；Then decline stove to crucible to cool down, make
The temperature of the bottom of silica crucible is down to 450~480 DEG C, then makes silica crucible in earthenware with the decrease speed of 0.01~2.0mm/h
Crucible declines to be declined in stove, until melt is frozen into solid；Crucible is set to decline stove cooling with the rate of temperature fall of 10~50 DEG C/h later,
Until being down to room temperature, rare earth halide scintillation crystal has so far been grown in silica crucible；Finally in dry environment, from quartz
The rare earth halide scintillation crystal prepared is taken out in crucible.
2. a kind of preparation method of rare earth halide scintillation crystal according to claim 1, it is characterised in that the step
In rapid one, raw material has CsCl, LiCl, LaCl3And CeCl3。
3. a kind of preparation method of rare earth halide scintillation crystal according to claim 1 or 2, it is characterised in that described
In step 2, the environment full of inert gas is the glove box full of inert gas.
4. a kind of preparation method of rare earth halide scintillation crystal according to claim 3, it is characterised in that the step
In rapid three, using molecular pump by silica crucible vacuum state；The silica crucible of vacuum state is welded using acetylene flame
Envelope.
5. a kind of preparation method of rare earth halide scintillation crystal any one of Claims 1-4 is prepared dilute
The application of native halide scintillation crystal, it is characterised in that the rare earth halide scintillation crystal is in neutron detection, gamma ray detection
Or the application in flash detection field.
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109576789A (en) * | 2018-12-29 | 2019-04-05 | 厦门中烁光电科技有限公司 | The processing method of cerium dopping rare earth halide monocrystalline |
| CN110004485A (en) * | 2019-04-26 | 2019-07-12 | 宁波大学 | A kind of scintillation crystal and preparation method thereof of rare earth element cerium dopping |
| CN113512757A (en) * | 2021-04-28 | 2021-10-19 | 山东大学 | Large-block high-quality scintillation crystal and preparation method and application thereof |
| CN113897666A (en) * | 2020-06-22 | 2022-01-07 | 中国科学院上海硅酸盐研究所 | Intrinsically luminous halide scintillation crystal and preparation method and application thereof |
| CN114411251A (en) * | 2022-01-20 | 2022-04-29 | 西北工业大学深圳研究院 | Method for growing high-quality CLLB crystal by using moving heater method |
| CN114958331A (en) * | 2022-05-05 | 2022-08-30 | 闽都创新实验室 | Double perovskite crystal and preparation method and application thereof |
| CN117070218A (en) * | 2023-10-16 | 2023-11-17 | 中国科学院上海硅酸盐研究所 | Copper-doped enhanced ionizing radiation luminescent halide scintillator, preparation method and application thereof |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103951240A (en) * | 2014-05-08 | 2014-07-30 | 宁波大学 | Rare-earth-ion-doped Cs2LiLaCl6 microcrystalline glass and preparation method thereof |
| CN106745163A (en) * | 2015-11-24 | 2017-05-31 | 有研稀土新材料股份有限公司 | High-pure anhydrous compound rare-earth halide and preparation method thereof |
| CN107366018A (en) * | 2017-07-12 | 2017-11-21 | 宁波大学 | A kind of rare earth halide mixing scintillation crystal and preparation method thereof |
| CN107794566A (en) * | 2017-10-31 | 2018-03-13 | 山东大学 | A kind of Ce detected for gamma-rays, neutron pair:Cs2LiYCl6The fast preparation method of crystal |
-
2018
- 2018-05-09 CN CN201810436170.2A patent/CN108531988A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103951240A (en) * | 2014-05-08 | 2014-07-30 | 宁波大学 | Rare-earth-ion-doped Cs2LiLaCl6 microcrystalline glass and preparation method thereof |
| CN106745163A (en) * | 2015-11-24 | 2017-05-31 | 有研稀土新材料股份有限公司 | High-pure anhydrous compound rare-earth halide and preparation method thereof |
| CN107366018A (en) * | 2017-07-12 | 2017-11-21 | 宁波大学 | A kind of rare earth halide mixing scintillation crystal and preparation method thereof |
| CN107794566A (en) * | 2017-10-31 | 2018-03-13 | 山东大学 | A kind of Ce detected for gamma-rays, neutron pair:Cs2LiYCl6The fast preparation method of crystal |
Non-Patent Citations (3)
| Title |
|---|
| JAREK GLODO等: "Selected Properties of Cs2LiYCl6, Cs2LiLaCl6, and Cs2LiLaBr6 Scintillators", 《IEEE TRANSACTIONS ON NUCLEAR SCIENCE》 * |
| P.A. RODNYI等: "Luminescence properties of Ce-doped Cs2LiLaCl6 crystals", 《JOURNAL OF LUMINESCENCE》 * |
| RUTA等: "Understanding phase equilibria and segregation in Bridaman growth of Cs2LiYCl6 scintillator", 《JOURNAL OF MATERIALS RESEARCH》 * |
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109576789A (en) * | 2018-12-29 | 2019-04-05 | 厦门中烁光电科技有限公司 | The processing method of cerium dopping rare earth halide monocrystalline |
| CN110004485A (en) * | 2019-04-26 | 2019-07-12 | 宁波大学 | A kind of scintillation crystal and preparation method thereof of rare earth element cerium dopping |
| CN113897666A (en) * | 2020-06-22 | 2022-01-07 | 中国科学院上海硅酸盐研究所 | Intrinsically luminous halide scintillation crystal and preparation method and application thereof |
| CN113512757A (en) * | 2021-04-28 | 2021-10-19 | 山东大学 | Large-block high-quality scintillation crystal and preparation method and application thereof |
| CN114411251A (en) * | 2022-01-20 | 2022-04-29 | 西北工业大学深圳研究院 | Method for growing high-quality CLLB crystal by using moving heater method |
| CN114958331A (en) * | 2022-05-05 | 2022-08-30 | 闽都创新实验室 | Double perovskite crystal and preparation method and application thereof |
| CN114958331B (en) * | 2022-05-05 | 2024-01-02 | 闽都创新实验室 | Double perovskite crystal and preparation method and application thereof |
| CN117070218A (en) * | 2023-10-16 | 2023-11-17 | 中国科学院上海硅酸盐研究所 | Copper-doped enhanced ionizing radiation luminescent halide scintillator, preparation method and application thereof |
| CN117070218B (en) * | 2023-10-16 | 2023-12-26 | 中国科学院上海硅酸盐研究所 | Copper-doped enhanced ionizing radiation luminescent halide scintillator, preparation method and application thereof |
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Application publication date: 20180914 |