CN103951242A - Rare-earth-ion-doped Cs2LiLaI6 microcrystalline glass and preparation method thereof - Google Patents

Rare-earth-ion-doped Cs2LiLaI6 microcrystalline glass and preparation method thereof Download PDF

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CN103951242A
CN103951242A CN201410198340.XA CN201410198340A CN103951242A CN 103951242 A CN103951242 A CN 103951242A CN 201410198340 A CN201410198340 A CN 201410198340A CN 103951242 A CN103951242 A CN 103951242A
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glass
lilai
devitrified glass
rare earth
earth ion
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CN103951242B (en
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杨斌
张约品
夏海平
王倩
欧阳绍业
张为欢
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Ningbo University
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Ningbo University
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Abstract

The invention discloses a rare-earth-ion-doped Cs2LiGdBr6 microcrystalline glass and a preparation method thereof. The microcrystalline glass is composed of the following components in percentage by mole: 65-75 mol% of TeO2, 10-15 mol% of ZnF2, 5-6 mol% of La2O3 and 9-15 mol% of Cs2LiLa(1-x)LnxI6, wherein x=0.01-0.1, and Ln is Ce<3+>, Eu<3+>, Tb<3+>, Pr<3+> or Nd<3+>. The preparation method comprises the following steps: preparing TeO2-ZnF2-La2O3-Cs2LiLa(1-x)LnxI6 glass by a fusion process, and carrying out heat treatment to obtain the transparent Cs2LiLaBr6 microcrystalline glass. The Cs2LiLaI6 microcrystalline glass has the advantages of deliquescence resistance, favorable mechanical properties, higher short-wavelength blue-violet light transmission rate, high flare light emission output, favorable energy resolution and the like. The preparation method of the microcrystalline glass is simple and lower in production cost.

Description

Rare earth ion doped Cs 2liLaI 6devitrified glass and preparation method thereof
Technical field
The present invention relates to a kind of rare earth ion doped devitrified glass, especially relate to a kind of rare earth ion doped Cs as scintillation material 2liLaI 6devitrified glass and preparation method thereof.
Background technology
Scintillation material is a kind of optical function material that can send visible ray under the exciting of energetic ray (as x ray, gamma-rays) or other radioactive particle, is widely used in the fields such as nuclear medicine diagnostic, high energy physics and nuclear physics experiment research, industry and geological prospecting.According to the difference of Application Areas, the requirement of scintillator is also not quite similar, but generally scintillation material should possess following properties: the features such as luminous efficiency is high, fluorescence decay is fast, density is large, cost is low and radiation resistance is good.Scintillation crystal generally has the advantages such as resistance to irradiation, fast decay, High Light Output, but scintillation crystal also exists following serious shortcoming: preparation difficulty, and expensive.Although and rare earth ion doped scintillation glass cost is low, easily prepare large-size glass, it is compared with crystal in aspect difficulties such as light output, multiplicity, so its application is also very limited.
Cs 2liLaI 6crystal is a kind of scintillation crystal matrix that can doping with rare-earth ions, Ce 3+the Cs of doping 2liLaI 6it is high that crystal has light output, decay soon, and good energy resolution, temporal resolution and linear response, have than rare earth ion doped crystal of fluoride and the higher luminous efficiency of oxide crystal, can make flash detection instrument efficiency greatly improve.Eu 3+, Tb 3+doping Cs 2liLaI 6the scintillation properties of crystal is also more excellent, can be used for the fields such as safety check, blinking screen.But Cs 2liLaI 6crystal is deliquescence very easily, and mechanical property is poor, easy cleavage slabbing, and large-size crystals growth difficulty, and expensively affected its practical application.
Summary of the invention
The technical problem to be solved in the present invention is to provide a kind of Deliquescence-resistant, good mechanical property, has extremely strong light output, fast decay, energy resolution and the good rare earth ion doped Cs of temporal resolution 2liLaI 6devitrified glass and preparation method thereof.
The present invention solves the problems of the technologies described above adopted technical scheme: rare earth ion doped Cs 2liLaI 6devitrified glass, its mole of percentage composition is:
TeO 2：65-75mol％ ZnF 2：10-15mol％
La 2o 3: 5-6mol% Cs 2liLa (1-x)ln xi 6: 9-15mol%, x=0.01-0.1 in formula, Ln is Ce 3+, Eu 3+, Tb 3+, Pr 3+, Nd 3+in a kind of rare earth ion.
This flicker devitrified glass material component is: TeO 2: 65mol%, ZnF 2: 15mol%, La 2o 3: 5mol%, Cs 2liLa 0.99ce 0.01i 6: 15mol%.
This flicker devitrified glass material component is: TeO 2: 70mol%, ZnF 2: 15mol%, La 2o 3: 6mol%, Cs 2liLa 0.9eu 0.1i 6: 9mol%.
This flicker devitrified glass material component is: TeO 2: 75mol%, ZnF 2: 10mol%, La 2o 3: 5mol%, Cs 2liLa 0.95tb 0.05i 6: 10mol%.
Described rare earth ion doped Cs 2liLaI 6the preparation method of devitrified glass, comprises the steps:
(1) TeO 2-ZnF 2-La 2o 3-Cs 2liLa (1-x)ln xi 6be founding of glass:
Cs 2liLa (1-x)ln xi 6raw material is by CsI, LiI, LaI 3, LnI 3mixed sintering forms, and by material component, takes analytically pure each raw material, respectively adds the NH that accounts for raw material gross weight 5% 4hF 2, NH 4hI 2raw material is mixed, then pour in quartz crucible or corundum crucible and melt, temperature of fusion 800-900 ℃, insulation 1-2 hour, glass melt is poured in pig mold, then glass is placed in to retort furnace and anneals, after glass transformation temperature Tg temperature is incubated 1 hour, with the speed of 10 ℃/h, be cooled to 50 ℃, close retort furnace power supply and be automatically cooled to room temperature, take out glass, for micritization thermal treatment.
(2) Cs 2liLaI 6devitrified glass preparation:
According to heat analysis (DTA) experimental data of glass, the glass making is placed in to nitrogen fine annealing stove, near its first crystallization peak, heat-treated is 4～6 hours, and then be cooled to 50 ℃ with the speed of 5 ℃/h, close fine annealing stove power supply, automatically be cooled to room temperature, obtain transparent rare earth ion doped Cs 2liLaI 6devitrified glass.
Compared with prior art, the invention has the advantages that: this devitrified glass is comprised of fluorine iodine oxygen compound, short wavelength's through performance is good, has Cs 2liLaI 6the superior scintillation properties of crystalline host material and physical strength, the stability of oxide glass and be easy to processing feature, overcome Cs 2liLaI 6single crystal is the shortcoming such as deliquescence, poor, the easy cleavage slabbing of mechanical property very easily; The experiment proved that: by formula of the present invention and preparation method, separate out rare earth ion doped to Cs 2liLaI 6crystalline phase, the rare earth ion doped Cs making 2liLaI 6devitrified glass is transparent, can Deliquescence-resistant, good mechanical property, short wavelength's royal purple light transmission rate be higher, has extremely strong light output, and decay soon, the performances such as good energy resolution and temporal resolution, can make nuclear detection instrument efficiency greatly improve.The preparation method of this devitrified glass is simple, and production cost is lower.
Accompanying drawing explanation
Fig. 1 is the transmission electron microscope figure (TEM) of sample after embodiment mono-micritization thermal treatment.
Fig. 2 is the Ce:Cs of embodiment mono-excitation of X-rays 2liLaI 6the fluorescence spectrum of devitrified glass.
Fig. 3 is the Eu:Cs of embodiment bis-excitation of X-rays 2liLaI 6the fluorescence spectrum of devitrified glass.
Fig. 4 is the Tb:Cs of embodiment tri-excitation of X-rays 2liLaI 6the fluorescence spectrum of devitrified glass.
Embodiment
Below in conjunction with accompanying drawing, embodiment is described in further detail the present invention.
Embodiment mono-: table 1 is glass formula and the first recrystallization temperature value of embodiment mono-.
Table 1
Concrete preparation process is as follows: the first step, Cs 2liLa 0.99ce 0.01i 6raw material is by CsI, LiI, LaI 3, CeI 3mixed sintering forms, and by the formula in table 1, weighs 50 grams of analytical pure raw materials, adds 2.5 grams of NH 4hF 2, 2.5 grams of NH 4hI 2after raw material is mixed, pour in quartz crucible and melt, 800 ℃ of temperature of fusion, be incubated 2 hours, glass melt is poured in pig mold, be then placed in retort furnace and anneal, after glass transformation temperature Tg temperature is incubated 1 hour, with the speed of 10 ℃/h, be cooled to 50 ℃, close retort furnace power supply and be automatically cooled to room temperature, take out glass; Second step, according to heat analysis (DTA) experimental data of glass, obtain 447 ℃ of the first recrystallization temperatures, the glass making is placed in to nitrogen fine annealing stove, 465 ℃ of thermal treatments 6 hours, and then be cooled to 50 ℃ with the speed of 5 ℃/h, and close fine annealing stove power supply and be automatically cooled to room temperature, obtain transparent Ce 3+the Cs of doping 2liLaI 6devitrified glass.
Cs to preparation 2liLaI 6devitrified glass carries out transmission electron microscope test, obtain the transmission electron microscope picture of glass after micritization is processed as shown in Figure 1, its result is as follows: in photo, glass basis seems more clearly with the nano microcrystalline of separating out, and the stain distributing in glass basis is microcrystal grain.X-ray diffraction test shows that crystalline phase is Cs 2liLaI 6phase, the material therefore obtaining is Cs 2liLaI 6the devitrified glass of crystallization phase.The Ce of excitation of X-rays 3+ion doping Cs 2liLaI 6as shown in Figure 2, fluorescence peak intensity is very large for the fluorescence spectrum of devitrified glass.Mix Ce 3+ion Cs 2liLaI 6the output of devitrified glass light can reach between 45000ph/MeV, and be 70ns fall time.
Embodiment bis-: table 2 is glass formula and the first recrystallization temperature value of embodiment bis-.
Table 2
Concrete preparation process is as follows: the first step, Cs 2liLa 0.9eu 0.1i 6raw material is by CsI, LiI, LaI 3, EuI 3mixed sintering forms, and by the formula in table 2, weighs 50 grams of analytical pure raw materials, adds 2.5 grams of NH 4hF 2, 2.5 grams of NH 4hI 2after raw material is mixed, pour in corundum crucible and melt, 900 ℃ of temperature of fusion, be incubated 1 hour, glass melt is poured in pig mold, be then placed in retort furnace and anneal, after glass transformation temperature Tg temperature is incubated 1 hour, with the speed of 10 ℃/h, be cooled to 50 ℃, close retort furnace power supply and be automatically cooled to room temperature, take out glass; Second step, according to heat analysis (DTA) experimental data of glass, obtain 449 ℃ of the first recrystallization temperatures, the glass making is placed in to nitrogen fine annealing stove, 468 ℃ of thermal treatments 4 hours, and then be cooled to 50 ℃ with the speed of 5 ℃/h, and close fine annealing stove power supply and be automatically cooled to room temperature, obtain transparent Eu 3+the Cs of ion doping 2liLaI 6devitrified glass.
Cs to preparation 2liLaI 6the spectral quality test of devitrified glass, the Eu of excitation of X-rays 3+ion doping Cs 2liLaI 6as shown in Figure 3, its result shows to produce Eu:Cs after Overheating Treatment to the fluorescence spectrum of devitrified glass 2liLaI 6crystallite is compared luminous intensity with corresponding glass basis and is significantly improved, and Eu:Cs is described 2liLaI 6the luminosity of devitrified glass is better.
Embodiment tri-: table 3 is glass formula and the first recrystallization temperature value of embodiment tri-.
Table 3
Concrete preparation process is as follows: the first step, Cs 2liLa 0.95tb 0.05i 6raw material is by CsI, LiI, LaI 3, TbI 3mixed sintering forms, and by the formula in table 3, weighs 50 grams of analytical pure raw materials, adds 2.5 grams of NH 4hF 2, 2.5 grams of NH 4hI 2after raw material is mixed, pour in quartz crucible and melt, 850 ℃ of temperature of fusion, be incubated 1.5 hours, glass melt is poured in pig mold, be then placed in retort furnace and anneal, after glass transformation temperature Tg temperature is incubated 1 hour, with the speed of 10 ℃/h, be cooled to 50 ℃, close retort furnace power supply and be automatically cooled to room temperature, take out glass.Second step, according to heat analysis (DTA) experimental data of glass, obtain 452 ℃ of the first recrystallization temperatures, the glass making is placed in to nitrogen fine annealing stove, 473 ℃ of thermal treatments 5 hours, and then be cooled to 50 ℃ with the speed of 5 ℃/h, and close fine annealing stove power supply and be automatically cooled to room temperature, obtain transparent Tb 3+the Cs of ion doping 2liLaI 6devitrified glass.
Cs to preparation 2liLaI 6the spectral quality test of devitrified glass, the Tb of excitation of X-rays 3+ion doping Cs 2liLaI 6as shown in Figure 4, its result shows to produce Tb:Cs after Overheating Treatment to the fluorescence spectrum of devitrified glass 2liLaI 6crystallite is compared luminous intensity with corresponding glass basis and is significantly improved, and Tb:Cs is described 2liLaI 6the luminosity of devitrified glass is better, and luminous intensity obviously improves; The rare earth ion doped Cs being obtained by above-mentioned preparation process 2liLaI 6devitrified glass is transparent and physical and chemical performance is good.
Embodiment 4
Substantially the same manner as Example 1, difference is material component difference: TeO 2: 75mol%, ZnF 2: 10mol%, La 2o 3: 5mol%, Cs 2liLa 0.95pr 0.05i 6: 10mol%.
Embodiment 5
Substantially the same manner as Example 1, difference is material component difference: TeO 2: 75mol%, ZnF 2: 10mol%, La 2o 3: 5mol%, Cs 2liLa 0.95nd 0.05i 6: 10mol%.
Embodiment 4,5 also can obtain rare earth ion doped Cs preferably 2liLaI 6devitrified glass, concrete flicker devitrified glass spectrum does not just provide one by one.

Claims (5)

1. a rare earth ion doped Cs 2liLaI 6devitrified glass, its mole of percentage composition is:
TeO 2：65-75mol％ ZnF 2：10-15mol％
La 2o 3: 5-6mol% Cs 2liLa (1-x)ln xi 6: 9-15mol%, x=0.01-0.1 in formula, Ln is Ce 3+, Eu 3+, Tb 3+, Pr 3+, Nd 3+in a kind of rare earth ion.
2. rare earth ion doped Cs claimed in claim 1 2liLaI 6devitrified glass, is characterized in that this flicker devitrified glass material component is: TeO 2: 65mol%, ZnF 2: 15mol%, La 2o 3: 5mol%, Cs 2liLa 0.99ce 0.01i 6: 15mol%.
3. rare earth ion doped Cs claimed in claim 1 2liLaI 6devitrified glass, is characterized in that this flicker devitrified glass material component is: TeO 2: 70mol%, ZnF 2: 15mol%, La 2o 3: 6mol%, Cs 2liLa 0.9eu 0.1i 6: 9mol%.
4. rare earth ion doped Cs claimed in claim 1 2liLaI 6devitrified glass, is characterized in that this flicker devitrified glass material component is: TeO 2: 75mol%, ZnF 2: 10mol%, La 2o 3: 5mol%, Cs 2liLa 0.95tb 0.05i 6: 10mol%.
5. rare earth ion doped Cs according to claim 1 2liLaI 6the preparation method of devitrified glass, is characterized in that comprising following concrete steps:
(1) TeO 2-ZnF 2-La 2o 3-Cs 2liLa (1-x)ln xi 6be founding of glass: Cs 2liLa (1-x)ln xi 6raw material is by CsI, LiI, LaI 3, LnI 3mixed sintering forms, and by material component, takes analytically pure each raw material, respectively adds the NH that accounts for raw material gross weight 5% 4hF 2, NH 4hI 2raw material is mixed, then pour in quartz crucible or corundum crucible and melt, temperature of fusion 800-900 ℃, insulation 1-2 hour, glass melt is poured in pig mold, be then placed in retort furnace and anneal, after glass transformation temperature Tg temperature is incubated 1 hour, with the speed of 10 ℃/h, be cooled to 50 ℃, close retort furnace power supply and be automatically cooled to room temperature, take out glass, for micritization thermal treatment;
(2) Cs 2liLaI 6the preparation of devitrified glass: according to the thermal analysis experiment data of glass, the glass making is placed in near nitrogen fine annealing stove heat-treated 4～6 hours its first crystallization peak, and then be cooled to 50 ℃ with the speed of 5 ℃/h, close fine annealing stove power supply, automatically be cooled to room temperature, obtain transparent rare earth ion doped Cs 2liLaI 6devitrified glass.
CN201410198340.XA 2014-05-08 2014-05-08 Rare earth ion doped Cs2liLaI6devitrified glass and preparation method thereof Expired - Fee Related CN103951242B (en)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105293919A (en) * 2015-11-16 2016-02-03 宁波大学 Glass film containing rare-earth-ion-doped Cs2LiLaI6 microcrystalline and preparation method thereof

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101913767A (en) * 2010-08-03 2010-12-15 宁波大学 Rare-earth doped oxyfluoride tellurate scintillation glass and preparation method thereof
US20130175475A1 (en) * 2011-11-24 2013-07-11 Vladimir Ouspenski Luminescent material and a process of forming the same

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101913767A (en) * 2010-08-03 2010-12-15 宁波大学 Rare-earth doped oxyfluoride tellurate scintillation glass and preparation method thereof
US20130175475A1 (en) * 2011-11-24 2013-07-11 Vladimir Ouspenski Luminescent material and a process of forming the same

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105293919A (en) * 2015-11-16 2016-02-03 宁波大学 Glass film containing rare-earth-ion-doped Cs2LiLaI6 microcrystalline and preparation method thereof

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