CN103951244A - Rare-earth-ion-doped Cs2LiYI6 microcrystalline glass and preparation method thereof - Google Patents

Abstract

The invention discloses a rare-earth-ion-doped Cs2LiYI6 microcrystalline glass and a preparation method thereof. The microcrystalline glass is composed of the following components in percentage by mole: 20-30 mol% of GeO2, 25-35 mol% of B2O3, 20-25 mol% of BaF2, 2-7 mol% of Y2O3 and 13-18 mol% of Cs2LiY(1-x)LnxI6, wherein x=0.05-0.2, and Ln is Ce<3+>, Eu<3+>, Tb<3+>, Pr<3+> or Nd<3+>. The preparation method comprises the following steps: preparing GeO2-B2O3-BaF2-Y2O3-Cs2LiY(1-x)LnxI6 glass by a fusion process, and carrying out heat treatment to obtain the transparent Cs2LiYI6 microcrystalline glass. The Cs2LiYI6 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 2liYI 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 ₂liYI 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 ₂liYI ₆crystal is a kind of scintillation crystal matrix that can doping with rare-earth ions, Ce ³⁺the Cs of doping ₂liYI 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 ₂liYI ₆the scintillation properties of crystal is also more excellent, can be used for the fields such as safety check, blinking screen.But Cs ₂liYI 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 stronger light output, fast decay, energy resolution and the good rare earth ion doped Cs of temporal resolution ₂liYI 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 ₂liYI ₆devitrified glass, its mole of percentage composition is:

GeO ₂：20-30mol％ B ₂O ₃：25-35mol％ BaF ₂：20-25mol％

Y ₂o ₃: 2-7mol% Cs ₂liY _(1-x)ln _xi ₆: 13-18mol%, x=0.05-0.2 in formula, Ln is Ce ³⁺, Eu ³⁺, Tb ³⁺, Pr ³⁺and Nd ³⁺in a kind of rare earth ion.

This flicker devitrified glass material component is: GeO ₂: 30mol%, B ₂o ₃: 25mol%, BaF ₂: 25mol%, Y ₂o ₃: 7mol%, Cs ₂liY _0.95ce _0.05i ₆: 13mol%.

This flicker devitrified glass material component is: GeO ₂: 25mol%, B ₂o ₃: 35mol%, BaF ₂: 20mol%, Y ₂o ₃: 5mol%, Cs ₂liY _0.8eu _0.2i ₆: 15mol%.

This flicker devitrified glass material component is: GeO ₂: 20mol%, B ₂o ₃: 35mol%, BaF ₂: 25mol%, Y ₂o ₃: 2mol%, Cs ₂liY _0.9tb _0.ii ₆: 18mol%.

Described rare earth ion doped YI ₃the preparation method of devitrified glass, comprises the steps:

(1) GeO ₂-B ₂o ₃-BaF ₂-Y ₂o ₃-Cs ₂liY _(1-x)ln _xi ₆be founding of glass:

Cs ₂liY _(1-x)ln _xi ₆raw material is by CsI, LiI, YI 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 1350-1480 ℃, 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 ₂liYI 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 ₂liYI 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 ₂liYI ₆the superior scintillation properties of crystalline host material and physical strength, the stability of oxide glass and be easy to processing feature, overcome Cs ₂liYI 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 ₂liYI ₆crystalline phase, the rare earth ion doped Cs making ₂liYI ₆devitrified glass is transparent, can Deliquescence-resistant, good mechanical property, short wavelength's royal purple light transmission rate be higher, has stronger light output, and decay soon, the performances such as good energy resolution and temporal resolution, can make flash 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 ₂liYI ₆the fluorescence spectrum of devitrified glass.

Fig. 3 is the Eu:Cs of embodiment bis-excitation of X-rays ₂liYI ₆the fluorescence spectrum of devitrified glass.

Fig. 4 is the Tb:Cs of embodiment tri-excitation of X-rays ₂liYI 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 ₂liY _0.95ce _0.05i ₆raw material is by CsI, LiI, YI 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, 1350 ℃ 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 680 ℃ of the first recrystallization temperatures, the glass making is placed in to nitrogen fine annealing stove 695 ℃ of thermal treatments 6 hours, and then be cooled to 50 ℃ with the speed of 5 ℃/h, close fine annealing stove power supply and be automatically cooled to room temperature, obtain transparent Ce ³⁺the Cs of doping ₂liYI ₆devitrified glass.

Cs to preparation ₂liYI 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 ₂liYI ₆phase, the material therefore obtaining is Cs ₂liYI ₆the devitrified glass of crystallization phase.The Ce of excitation of X-rays ³⁺ion doping Cs ₂liYI ₆as shown in Figure 2, fluorescence peak intensity is very large for the fluorescence spectrum of devitrified glass.Mix Ce ³⁺ion Cs ₂liYI ₆devitrified glass light is output as 33000ph/MeV, and be 50ns 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 ₂liY _0.8eu _0.2i ₆raw material is by CsI, LiI, YI 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, 1480 ℃ 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 690 ℃ of the first recrystallization temperatures, the glass making is placed in to nitrogen fine annealing stove 705 ℃ of thermal treatments 4 hours, and then be cooled to 50 ℃ with the speed of 5 ℃/h, close fine annealing stove power supply and be automatically cooled to room temperature, obtain transparent Eu ³⁺the Cs of ion doping ₂liYI ₆devitrified glass.

Cs to preparation ₂liYI ₆the spectral quality test of devitrified glass, the Eu of excitation of X-rays ³⁺ion doping Cs ₂liYI ₆as shown in Figure 3, its result shows to produce Eu: Cs after Overheating Treatment to the fluorescence spectrum of devitrified glass ₂liYI ₆crystallite is compared luminous intensity with corresponding glass basis and is significantly improved, and Eu is described: Cs ₂liYI 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 ₂liY _0.95ce _0.05i ₆raw material is by CsI, LiI, YI 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, 1450 ℃ 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 695 ℃ of the first recrystallization temperatures, the glass making is placed in to nitrogen fine annealing stove 715 ℃ of thermal treatments 4 hours, and then be cooled to 50 ℃ with the speed of 5 ℃/h, close fine annealing stove power supply and be automatically cooled to room temperature, obtain transparent Tb ³⁺the Cs of ion doping ₂liYI ₆devitrified glass.

Cs to preparation ₂liYI ₆the spectral quality test of devitrified glass, the Tb of excitation of X-rays ³⁺ion doping Cs ₂liYI ₆as shown in Figure 4, its result shows to produce Tb: Cs after Overheating Treatment to the fluorescence spectrum of devitrified glass ₂liYI ₆crystallite is compared luminous intensity with corresponding glass basis and is significantly improved, and Tb is described: Cs ₂liYI ₆the luminosity of devitrified glass is better; The rare earth ion doped Cs being obtained by above-mentioned preparation process ₂liYI 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: GeO ₂: 20mol%, B ₂o ₃: 35mol%, BaF ₂: 25mol%, Y ₂o ₃: 2mol%, Cs ₂liY _0.9pr _0.1i ₆: 18mol%.

Embodiment 5

Substantially the same manner as Example 1, difference is material component difference: GeO ₂: 20mol%, B ₂o ₃: 35mol%, BaF ₂: 25mol%, Y ₂o ₃: 2mol%, Cs ₂liY _0.9nd _0.1i ₆: 18mol%.

Embodiment 4,5 also can obtain rare earth ion doped Cs preferably ₂liYI ₆devitrified glass, concrete flicker devitrified glass spectrum does not just provide one by one.

Claims (5)

1. a rare earth ion doped Cs ₂liYI ₆devitrified glass, its mole of percentage composition is:

GeO ₂：20-30mol％ B ₂O ₃：25-35mol％ BaF ₂：20-25mol％

Y ₂o ₃: 2-7mol% Cs ₂liY _(1-x)ln _xi ₆: 13-18mol%, x=0.05-0.2 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 ₂liYI ₆devitrified glass, is characterized in that this flicker devitrified glass material component is: GeO ₂: 30mol%, B ₂o ₃: 25mol%, BaF ₂: 25mol%, Y ₂o ₃: 7mol%, Cs ₂liY _0.95ce _0.05i ₆: 13mol%.

3. rare earth ion doped Cs claimed in claim 1 ₂liYI ₆devitrified glass, is characterized in that this flicker devitrified glass material component is: GeO ₂: 25mol%, B ₂o ₃: 35mol%, BaF ₂: 20mol%, Y ₂o ₃: 5mol%, Cs ₂liY _0.8eu _0.2i ₆: 15mol%.

4. rare earth ion doped Cs claimed in claim 1 ₂liYI ₆devitrified glass, is characterized in that this flicker devitrified glass material component is: GeO ₂: 20mol%, B ₂o ₃: 35mol%, BaF ₂: 25mol%, Y ₂o ₃: 2mol%, Cs ₂liY _0.9tb _0.1i ₆: 18mol%.

5. rare earth ion doped Cs according to claim 1 ₂liYI ₆the preparation method of devitrified glass, is characterized in that comprising following concrete steps:

(1) GeO ₂-B ₂o ₃-BaF ₂-Y ₂o ₃-Cs ₂liY _(1-x)ln _xi ₆be founding of glass: Cs ₂liY _(1-x)ln _xi ₆raw material is by CsI, LiI, YI 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 1350-1480 ℃, 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 ₂liYI ₆the preparation of devitrified glass: according to heat analysis (DTA) experimental 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 ₂liYI ₆devitrified glass.