CN101701154B - Brominated rare earth scintillating materials and preparation method of Brominated rare earth scintillating crystals - Google Patents
Brominated rare earth scintillating materials and preparation method of Brominated rare earth scintillating crystals Download PDFInfo
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- CN101701154B CN101701154B CN2009101981390A CN200910198139A CN101701154B CN 101701154 B CN101701154 B CN 101701154B CN 2009101981390 A CN2009101981390 A CN 2009101981390A CN 200910198139 A CN200910198139 A CN 200910198139A CN 101701154 B CN101701154 B CN 101701154B
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- 239000013078 crystal Substances 0.000 title claims abstract description 131
- 229910052761 rare earth metal Inorganic materials 0.000 title claims abstract description 56
- 150000002910 rare earth metals Chemical class 0.000 title claims abstract description 56
- 239000000463 material Substances 0.000 title claims abstract description 33
- 238000002360 preparation method Methods 0.000 title claims abstract description 26
- 229910052688 Gadolinium Inorganic materials 0.000 claims abstract description 8
- 229910052746 lanthanum Inorganic materials 0.000 claims abstract description 8
- 239000000126 substance Substances 0.000 claims abstract description 7
- 239000010453 quartz Substances 0.000 claims description 24
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 24
- 238000000034 method Methods 0.000 claims description 21
- 239000002994 raw material Substances 0.000 claims description 13
- 238000012545 processing Methods 0.000 claims description 9
- 230000007423 decrease Effects 0.000 claims description 8
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 8
- 239000012467 final product Substances 0.000 claims description 7
- 238000002156 mixing Methods 0.000 claims description 7
- 239000000919 ceramic Substances 0.000 claims description 4
- 229910052697 platinum Inorganic materials 0.000 claims description 4
- 239000000843 powder Substances 0.000 claims description 4
- 239000011449 brick Substances 0.000 claims description 3
- 229910052727 yttrium Inorganic materials 0.000 abstract description 4
- 239000000203 mixture Substances 0.000 abstract description 2
- 230000000052 comparative effect Effects 0.000 description 27
- 238000001035 drying Methods 0.000 description 10
- 238000012360 testing method Methods 0.000 description 8
- 229910017768 LaF 3 Inorganic materials 0.000 description 7
- XKUYOJZZLGFZTC-UHFFFAOYSA-K lanthanum(iii) bromide Chemical compound Br[La](Br)Br XKUYOJZZLGFZTC-UHFFFAOYSA-K 0.000 description 6
- 229910052684 Cerium Inorganic materials 0.000 description 5
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 description 5
- 239000002019 doping agent Substances 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 238000011160 research Methods 0.000 description 5
- 238000007789 sealing Methods 0.000 description 5
- 238000001228 spectrum Methods 0.000 description 4
- OLAJVGIKTMFHDM-UHFFFAOYSA-K [Br-].[La+3].[F].[Br-].[Br-] Chemical compound [Br-].[La+3].[F].[Br-].[Br-] OLAJVGIKTMFHDM-UHFFFAOYSA-K 0.000 description 3
- 230000005284 excitation Effects 0.000 description 3
- UIWYJDYFSGRHKR-UHFFFAOYSA-N gadolinium atom Chemical compound [Gd] UIWYJDYFSGRHKR-UHFFFAOYSA-N 0.000 description 3
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 description 3
- 239000005022 packaging material Substances 0.000 description 3
- 238000012856 packing Methods 0.000 description 3
- VWQVUPCCIRVNHF-UHFFFAOYSA-N yttrium atom Chemical compound [Y] VWQVUPCCIRVNHF-UHFFFAOYSA-N 0.000 description 3
- 230000002950 deficient Effects 0.000 description 2
- 238000001514 detection method Methods 0.000 description 2
- 238000000295 emission spectrum Methods 0.000 description 2
- 238000005538 encapsulation Methods 0.000 description 2
- 238000009206 nuclear medicine Methods 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 1
- AGONCBOTBXYTGA-UHFFFAOYSA-H cerium(3+) lanthanum(3+) hexabromide Chemical compound [Br-].[Ce+3].[La+3].[Br-].[Br-].[Br-].[Br-].[Br-] AGONCBOTBXYTGA-UHFFFAOYSA-H 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000002109 crystal growth method Methods 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000004927 fusion Effects 0.000 description 1
- 230000005251 gamma ray Effects 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000007689 inspection Methods 0.000 description 1
- 230000005658 nuclear physics Effects 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 230000000750 progressive effect Effects 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
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Abstract
The invention discloses a brominated rare earth scintillating material with the chemical composition as follows: (1-a-b) ReBr3.aCeBr3.bReF3, wherein Re is one or a plurality of the elements La, Gd and Y; a is greater than or equal to 0.001% and less than or equal to 50%, b is greater than or equal to 0.001% and less than or equal to 50%, and a is not equal to b. The brominated rare earth scintillating material has good deliquescence proof performance, highlight output, rapid attenuation and better energy resolution, thus greatly widening the used space and application field of the brominated rare earth scintillating material. The invention also relates to a preparation method of the brominated rare earth scintillating crystals.
Description
Technical field
The present invention relates to the preparation method of a kind of brominated rare earth scintillating materials and Brominated rare earth scintillating crystals.
Background technology
Scintillation crystal is meant the crystal that under ray (x ray, gamma-rays etc.) or high energy particle effect, can send ultraviolet or visible light.Cooperate follow-up electronics to convert ray that is invisible to the naked eye or particle to accessible signal or image by scintillation detectors that photo-detector constituted such as scintillation crystal, PM or silicon photo diodes, be widely used in fields such as high energy physics and nuclear physics, nuclear medicine, safety inspection, nuclear industry.
1984; RobertHofstadter finds the good scintillation properties of NaI crystal, has opened the prelude of scintillation crystal research, henceforth; The research of scintillation crystal has obtained develop rapidly, the scintillation crystal of tens of kinds of representative excellent propertys successively occurred.The NaI of the 1950's and CsI are the representatives of first-generation scintillation crystal, and they have the characteristics of high light output, but their density is lower, and relatively low to gamma-ray detection efficient, its twilight sunset phenomenon makes that its single photon counting rate is lower in addition.S-generation scintillation crystal is with the Bi of the seventies in 20th century
4Ge
3O
12Crystal is representative, and it is to use one of scintillation crystal the most widely at present, and it has higher density and short attenuation length, but its light output is relatively low, and twilight sunset is long, and energy resolution is also relatively poor.Third generation scintillation crystal is with the PbWO of the seventies in 20th century
4(being called for short PWO), Lu
2Si
2O
7(being called for short LSO) is representative, and the PWO crystal almost possesses all characteristics of excellent scintillation crystal, but because its light output stage is low, can only be used for exporting the lower high energy field that requires for light; The LSO crystal is one of best scintillation crystal of present over-all properties, and it has high-density, high light output; Characteristics such as fast decay, but its energy resolution is relatively poor, in addition; LSO crystal growth fusing point is up to 2050 ℃, and crystal growth is difficult, and the crystal homogeneity of growth is also relatively poor.In recent years, found that several kinds have the output of high light, the Brominated rare earth scintillating crystals of energy resolution and fast attenuation characteristic preferably concurrently.Wherein, mix cerium lanthanum bromide (LaBr
3: Ce) crystal is a found crystal at the beginning of 21 century, and it has high light output, fast decay, good characteristics such as energy resolution, be considered to the 4th generation scintillation crystal the representative crystal.For example; Chinese patent 200610064013.0,200710105857.X and 01804362.3 etc. are the correlative study of lanthanum bromide scintillation crystal; But the emphasis point of its research all is the performance of lanthanum bromide scintillation crystal own, and like the output of high light, aspect such as decay and energy resolution soon, these lanthanum bromide scintillation crystals are deliquescence very easily; In a single day plane of crystal contacts just dissolving rapidly with steam, bring big difficulty to crystal processing, performance study and practical application.Usually, the method that solves this type of problem in the world is at the plane of crystal plated film or utilizes vacuum or extremely encapsulation under the dry environment, these way complex process, and cost is high, and the plated film plane of crystal is in a single day impaired, and deliquescence will cause crystal damage rapidly.
Likewise, the powder of existing brominated rare earth scintillating materials or ceramic body also exist the very easily defective of deliquescence and difficult treatment.
Therefore, the moisture resistance that how effectively to strengthen brominated rare earth scintillating materials also is that domestic and international crystal scientific research personnel endeavours one of research and problem demanding prompt solution.
Summary of the invention
Technical problem to be solved by this invention is to have overcome very easily deliquescence of existing brominated rare earth scintillating materials; Thereby produce the defective of crystal processing and difficult treatment; Provide a kind of and had good anti-deliquescence performance and still have the output of high light, the decay and the better brominated rare earth scintillating materials and preparation method thereof of energy resolution soon, widened the usage space and the Application Areas of brominated rare earth scintillating materials thus greatly.
Brominated rare earth scintillating materials of the present invention, its chemical constitution is: (1-a-b) ReBr
3ACeBr
3BReF
3, wherein, Re is one or more among element La (lanthanum), Gd (gadolinium) and the Y (yttrium); 0.001%≤a≤50%, 0.001%≤b≤50%, and a ≠ b.
Preferably, brominated rare earth scintillating materials of the present invention is a Brominated rare earth scintillating crystals, and its chemical constitution is: (1-a-b) ReBr
3ACeBr
3BReF
3, wherein, Re is one or more among element La (lanthanum), Gd (gadolinium) and the Y (yttrium); 0.001%≤a≤50%, 0.001%≤b≤50%, and a ≠ b.
That wherein, described Re is preferable is element La.
Wherein, what the scope of described a was preferable is 0.001%≤a≤10%, and better is 0.001%≤a≤5%, and best a is 0.5%.
Wherein, what the scope of described b was preferable is 0.001%≤b≤10%, and better is 0.001%≤b≤5%, and best b is 2%.
In the present invention's one preferred embodiments, brominated rare earth scintillating materials of the present invention is a Brominated rare earth scintillating crystals, and its chemical constitution is: (1-a-b) ReBr
3ACeBr
3BReF
3, wherein, Re is one or more among element La (lanthanum), Gd (gadolinium) and the Y (yttrium); 0.5%≤a≤2%, 2%≤b≤5%, and a ≠ b.
Also contain the conventional impurity of some this area brominated rare earth scintillating materials in the scintillation material of the present invention inevitably, like alkali gold dollar element, alkali earth metal or other REEs etc.
Brominated rare earth scintillating materials of the present invention both can be Brominated rare earth flicker powder, Brominated rare earth scintillating ceramic body, also can be transparent Brominated rare earth scintillating crystals, and the material of preparation all has anti-deliquescence performance equally.Wherein, preferable is Brominated rare earth scintillating crystals.Powder and ceramic body preparation method are simple and easy to realize, raw material fusion postcooling under vacuum condition are got final product.The preparation of Brominated rare earth scintillating crystals is then comparatively complicated.Wherein, the application of brominated rare earth scintillating materials is limited to transparent Brominated rare earth scintillating crystals mostly, size is generally greater than 1cm
3
The invention still further relates to a kind of preparation method of Brominated rare earth scintillating crystals, it comprises the steps: raw material ReBr
3, CeBr
3And ReF
3After the mixing, under vacuum state, adopt falling crucible method to carry out crystal growth, can make Brominated rare earth scintillating crystals; Wherein, Re is one or more among element La, Gd and the Y; Described CeBr
3Consumption be 0.001%～50%; Described ReF
3Consumption be 0.001%～50%; Described CeBr
3Consumption and ReF
3Consumption unequal; Described ReBr
3For surplus is supplied mol ratio 100%; Per-cent accounts for the molar percentage of raw material total amount for each raw material.
Wherein, described falling crucible method has another name called bridgeman crystal growth method (Bridgman-Stockbarge method) for existing method; This method places crucible for being used for the material that crystal growth uses, and descends lentamente, through a process furnace with certain temperature gradient; Separate through the gradient brick between the high temperature of process furnace and the cold zone, Control for Kiln Temperature is near the fusing point a little more than material, through heating region the time; Material in the crucible is melted, and treats in the crucible after the material temperature balance, when crucible continues to descend then; The temperature of crucible bottom drops to earlier below the fusing point, begins crystallization thus, and crystal continues to grow up with crucible decline then.What wherein, described crucible was preferable is the quartz crucible of quartz crucible or liner platinum crucible; What the processing parameter of described falling crucible method was preferable is: what the control furnace temperature was preferable is 950～1050 ℃, and that the temperature rise rate of furnace temperature is preferable is 60～100 ℃/h; The crucible bottom most position is in about the downward 20mm in gradient brick upper edge; That the thermograde of crystal growth interface is preferable is 20～50 ℃/cm; That the speed that described crucible descends is preferable is 0.2～2.0mm/h; After crucible decline stopped, the body of heater rate of temperature fall was 20～50 ℃/h.Wherein, the device that uses of described falling crucible method is the conventional crystal growing apparatus that uses in this area.
Among the present invention, above-mentioned each technical characterictic can arbitrary combination, promptly gets preferred embodiments of the present invention.
Agents useful for same of the present invention and raw material are all commercially available to be got.
Positive progressive effect of the present invention is: the present invention relates to a kind of Brominated rare earth scintillating crystals and preparation method thereof.This Brominated rare earth scintillating crystals has good anti-deliquescence performance, even in air, place the long period, the surface of this material still can keep better chemical stability and physics gloss; Thereby crystal is processed and encapsulation need not in utmost point dry environments such as vacuum or protection gas, to carry out; Reduce the crystalline preparation cost greatly, and the scintillation properties of this scintillation crystal is excellent; Having high light exports, decays soon and better energy resolution; Can detect X ray, gamma-rays, be applicable to fields such as nuclear medicine PET, radiation safety detection and geological exploration, widen the usage space and the Application Areas of Brominated rare earth scintillating crystals greatly.
Description of drawings
The energy resolution test spectrogram of the Brominated rare earth scintillating crystals that Fig. 1 makes for embodiment 1.
The energy resolution test spectrogram of the Brominated rare earth scintillating crystals that Fig. 2 makes for comparative example 1.
The energy resolution test spectrogram of the Brominated rare earth scintillating crystals that Fig. 3 makes for comparative example 2.
Spectrogram fall time of the Brominated rare earth scintillating crystals that Fig. 4 makes for embodiment 1.
Spectrogram fall time of the Brominated rare earth scintillating crystals that Fig. 5 makes for comparative example 1.
Spectrogram fall time of the Brominated rare earth scintillating crystals that Fig. 6 makes for comparative example 2.
Fig. 7 is the burst of ultraviolel emmission spectrum figure of the Brominated rare earth scintillating crystals that makes of embodiment 1, comparative example 1 and comparative example's 2 methods; Wherein, the crystal that A makes for embodiment 1, the crystal that B makes for comparative example 1, the crystal that C makes for comparative example 2; Ex representes the spectrogram that excites of sample, and em is the emission spectrogram of sample.
Fig. 8 is the physical condition of embodiment 1, comparative example 1 and comparative example's 2 methods plane of crystal when preparing crystal and just having gone out crucible.
Fig. 9 is that embodiment 1, comparative example 1 and comparative example's 2 methods prepare crystal to place humidity be the physical condition of 60% condition plane of crystal after following 5 minutes.
Embodiment
Mode through embodiment further specifies the present invention below, but does not therefore limit the present invention among the described scope of embodiments.
1 one inches 97.5%LaBr of embodiment
30.5%CeBr
32%LaF
3Crystal
Concrete preparation method is following:
(1) with anhydrous LaBr
3With doping agent CeBr
3And LaF
3By 97.5: 0.5: 2 the full and uniform mixing of mol ratio, in drying shed with the above raw material preprepared quartz crucible of packing into;
(2) the quartz crucible opening end is inserted vacuum pump and be evacuated to 10
-3Pa, sealing places quartz crucible in the crucible decline stove then and carries out crystal growth; Control for Kiln Temperature is at 1000 ℃ during growth, and crystal growth rate is controlled to be 1mm/h, and whole crystal growing process is 7-8 days; Crystal growth finishes, and treats that furnace temperature is reduced to take out quartz crucible after the room temperature and get final product.
In drying shed, break crucible into pieces, take out crystal, gained blank crystal perfection is transparent, and the long 4cm of equal-diameter part can obtain being of a size of the cerium doped with fluorine lanthanum bromide crystal of φ 25.4 * 25.4mm after the processing.
One inch 94%LaBr of embodiment 2 preparations
31%CeBr
35%LaF
3Crystal
Concrete preparation method is following:
(1) with the anhydrous LaBr of 100 grams
3With doping agent CeBr
3And LaF
3By 94: 1: 5 the full and uniform mixing of mol ratio, in drying shed, above raw material is packed in the quartz crucible of preprepared liner platinum crucible;
(2) the quartz crucible opening end is inserted vacuum pump and be evacuated to 10
-3Pa, sealing places quartz crucible in the crucible decline stove then and carries out crystal growth; Control for Kiln Temperature is at 1030 ℃ during growth, and crystal growth rate is controlled to be 0.8mm/h, and whole crystal growing process is 9-10 days; Crystal growth finishes, and treats that furnace temperature is reduced to take out quartz crucible after the room temperature and get final product.
In drying shed, break crucible into pieces, take out crystal, gained blank crystal perfection is transparent, and the long 4cm of equal-diameter part can obtain being of a size of the cerium doped with fluorine lanthanum bromide crystal of φ 25.4 * 25.4mm after the processing.
1.5 inches 94.5%LaBr of embodiment 3 preparations
30.5%CeBr
35%LaF
3Crystal
Concrete preparation method is following:
(1) with the anhydrous LaBr of 300 grams
3With doping agent CeBr
3And LaF
3By 94.5: 0.5: 5 the full and uniform mixing of mol ratio, in drying shed, above raw material is packed in the quartz crucible of preprepared liner platinum crucible;
(2) the quartz crucible opening end is inserted vacuum pump and be evacuated to 10
-3Pa, sealing places quartz crucible in the crucible decline stove then and carries out crystal growth; Control for Kiln Temperature is at 1050 ℃ during growth, and crystal growth rate is controlled to be 0.5mm/h, and whole crystal growing process is 15-16 days; Crystal growth finishes, and treats that furnace temperature is reduced to take out quartz crucible after the room temperature and get final product.
In drying shed, break crucible into pieces, take out crystal, gained blank crystal perfection is transparent, and the long 5cm of equal-diameter part can obtain being of a size of the cerium doped with fluorine lanthanum bromide crystal of φ 38 * 38mm after the processing.
Comparative example 199.5%LaBr
30.5%CeBr
3Crystal preparation (with reference to patent)
Concrete preparation method is following:
(1) with the anhydrous LaBr of 100 grams
3With doping agent CeBr
3By 99.5: 0.5 the full and uniform mixing of mol ratio, in drying shed with the above raw material preprepared quartz crucible of packing into;
(2) the quartz crucible opening end is inserted vacuum pump and be evacuated to 10
-3Pa, sealing places quartz crucible in the crucible decline stove then and carries out crystal growth; Control for Kiln Temperature is at 1000 ℃ during growth, and crystal growth rate is controlled to be 1mm/h, and whole crystal growing process is 7-8 days; Crystal growth finishes, and treats that furnace temperature is reduced to take out quartz crucible after the room temperature and get final product.
In drying shed, break crucible into pieces, take out crystal, gained blank crystal perfection is transparent, and the long 3cm of equal-diameter part can obtain being of a size of the cerium doping lanthanum bromide crystal of φ 25.4 * 25.4mm after the processing.
Comparative example 299.5%LaBr
30.5%CeF
3
Concrete preparation method is following:
(1) with the anhydrous LaBr of 100 grams
3With doping agent CeF
3By 99.5: 0.5 the full and uniform mixing of mol ratio, in drying shed with the above raw material preprepared quartz crucible of packing into;
(2) the quartz crucible opening end is inserted vacuum pump and be evacuated to 10
-3Pa, sealing places quartz crucible in the crucible decline stove then and carries out crystal growth; Control for Kiln Temperature is at 1000 ℃ during growth, and crystal growth rate is controlled to be 1mm/h, and whole crystal growing process is 7-8 days; Crystal growth finishes, and treats that furnace temperature is reduced to take out quartz crucible after the room temperature and get final product.
In drying shed, break crucible into pieces, take out crystal, gained blank crystal perfection is transparent, and the long 3mm of equal-diameter part can obtain being of a size of the cerium doping lanthanum bromide crystal of φ 25.4 * 25.4mm after the processing.
The test of effect embodiment 1 power spectrum
The crystal of getting embodiment 1 and comparative example 1 and 2 preparations carries out the power spectrum test respectively, adopts the multichannel pulse amplitude analysis system to join R980 type PM crystal is tested, the visible accompanying drawing 1～3 of result.Embodiment 1 as shown in Figure 1 makes the crystalline energy resolution and reaches 3.3%; It is 3.2% that comparative example 1 as shown in Figure 2 makes the crystalline energy resolution; It is 3.5% that comparative example 2 as shown in Figure 3 makes the crystalline energy resolution, shows thus to make crystalline energy resolution and comparative example by embodiment 1 to make crystal suitable basically.
Effect embodiment tests for 2 fall times
Adopt FLS920 type XRF that the crystal of embodiment 1 and comparative example 1 and 2 preparations is carried out the test of pl-spectrum fall time, the visible accompanying drawing 4～6 of result respectively.Embodiment 1 as shown in Figure 4 makes crystal, is measuring during for 340nm with IRF-EX, and it is 15.53ns that fitting result gets fall time; Comparative example 1 as shown in Figure 5 makes crystal, is measuring during for 313nm with IRF-EX, and it is 15.17ns that fitting result gets fall time; Comparative example 2 as shown in Figure 6 makes crystal, is measuring during for 342nm with IRF-EX, and it is 16.65ns that fitting result gets fall time; Show thus and make crystalline fall time and comparative example by embodiment 1 to make crystal suitable basically.
Effect embodiment 3 burst of ultraviolel emission spectrums
Adopt the LS50B type UVF spectrograph difference test implementation example 1 of the outfit Hamamatsu R928HA of company type PM and the crystalline burst of ultraviolel emission spectrum of comparative example 1 and 2 preparations, the result sees accompanying drawing 7.Shown in Fig. 7 A, embodiment 1 makes the crystal excitation peak and is positioned at 325nm, and emission peak lays respectively near 360nm and the 380nm; Shown in Fig. 7 B, comparative example 1 makes the crystal excitation peak and is positioned at 328nm, and emission peak lays respectively near 360nm and the 380nm; Shown in Fig. 7 C, comparative example 2 makes the crystal excitation peak and is positioned at 332nm, and emission peak lays respectively near 360nm and the 380nm; Show thus and make crystalline excitation-emission and comparative example by embodiment 1 to make crystal suitable basically.
Effect embodiment 4 deliquescence performance tests
Each fritter of crystal of getting embodiment 1 and comparative example 1 and 2 preparations carries out deliquescence relatively: the original state photo that Fig. 8 has just taken out from crucible for crystal; Fig. 9 is 60% for crystal in humidity, places the state photo after 5 minutes when temperature is 30 ℃.From figure, can obviously see crystal doping 2%LaF
3And 0.5%CeBr
3Back crystalline deliquescence performance is than doping 0.5%CeBr
3Or doping 0.5%CeF
3The lanthanum bromide crystal improvement is clearly all arranged.
Claims (10)
1. brominated rare earth scintillating materials, it is characterized in that: its chemical constitution is:
(1-a-b) ReBr
3ACeBr
3BReF
3, wherein, Re is one or more among element La, Gd and the Y; 0.001%≤a≤50%, 0.001%≤b≤50%, and a ≠ b, wherein, a, b are molar percentage.
2. brominated rare earth scintillating materials as claimed in claim 1 is characterized in that: described Re is element La.
3. brominated rare earth scintillating materials as claimed in claim 1 is characterized in that: the scope of described a is 0.001%≤a≤10%; The scope of described b is 0.001%≤b≤10%.
4. brominated rare earth scintillating materials as claimed in claim 3 is characterized in that: the scope of described a is 0.001%≤a≤5%; The scope of described b is 0.001%≤b≤5%.
5. brominated rare earth scintillating materials as claimed in claim 4 is characterized in that: the value of described a is 0.5%; The value of described b is 2%.
6. like each described brominated rare earth scintillating materials of claim 1～5, it is characterized in that: described brominated rare earth scintillating materials is Brominated rare earth flicker powder, Brominated rare earth scintillating ceramic body or a Brominated rare earth scintillating crystals.
7. brominated rare earth scintillating materials as claimed in claim 6 is characterized in that: described brominated rare earth scintillating materials is a Brominated rare earth scintillating crystals, and chemical constitution is: (1-a-b) ReBr
3ACeBr
3BReF
3, wherein, Re is one or more among element La, Gd and the Y; 0.5%≤a≤2%, 2%≤b≤5%, and a ≠ b.
8. the preparation method of a Brominated rare earth scintillating crystals as claimed in claim 6, it is characterized in that: it comprises the steps: raw material ReBr
3, CeBr
3And ReF
3After the mixing, under vacuum state, adopt falling crucible method to carry out crystal growth, get final product; Wherein, described Re is one or more among element La, Gd and the Y; Described CeBr
3Consumption be 0.001%～50%; Described ReF
3Consumption be 0.001%～50%; Described CeBr
3Consumption and ReF
3Consumption unequal; Described ReBr
3For surplus is supplied mol ratio 100%; Per-cent accounts for the molar percentage of raw material total amount for each raw material.
9. preparation method as claimed in claim 8 is characterized in that: the processing parameter of described falling crucible method is: the control furnace temperature is 950～1050 ℃, and the temperature rise rate of furnace temperature is 60～100 ℃/h; The crucible bottom most position is downward 20mm in gradient brick upper edge; The thermograde of crystal growth interface is 20～50 ℃/cm; The speed that described crucible descends is 0.2～2.0mm/h; After crucible decline stopped, the body of heater rate of temperature fall was 20～50 ℃/h.
10. preparation method as claimed in claim 8 is characterized in that: described crucible is the quartz crucible of quartz crucible or liner platinum crucible.
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| CN103695002B (en) * | 2013-12-26 | 2016-03-30 | 有研稀土新材料股份有限公司 | Inorganic scintillation material |
| CN107366018B (en) * | 2017-07-12 | 2019-05-21 | 宁波大学 | A kind of rare earth halide mixing scintillation crystal and preparation method thereof |
| CN112817031A (en) * | 2020-12-29 | 2021-05-18 | 北京跃成光子科技有限公司 | Method for efficiently preparing lanthanum-cerium bromide scintillation crystal array |
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| CN1404522A (en) * | 2000-02-17 | 2003-03-19 | 科学技术基金会 | Scintillator crystals, method for making same, use thereof |
| CN1798989A (en) * | 2003-06-05 | 2006-07-05 | 科学技术基金会 | Rare-earth iodide scintillation crystals |
| CN101054522A (en) * | 2007-06-01 | 2007-10-17 | 北京玻璃研究院 | Cerium activated rare earth halide bromide scintillator and preparing method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1404522A (en) * | 2000-02-17 | 2003-03-19 | 科学技术基金会 | Scintillator crystals, method for making same, use thereof |
| CN1798989A (en) * | 2003-06-05 | 2006-07-05 | 科学技术基金会 | Rare-earth iodide scintillation crystals |
| CN101054522A (en) * | 2007-06-01 | 2007-10-17 | 北京玻璃研究院 | Cerium activated rare earth halide bromide scintillator and preparing method thereof |
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