CN102021651A - Cerium-doped rare earth borate scintillating crystal and Bridgman preparation method thereof - Google Patents
Cerium-doped rare earth borate scintillating crystal and Bridgman preparation method thereof Download PDFInfo
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Abstract
The invention relates to the field of crystals, in particular to a cerium-doped rare earth borate scintillating crystal and a Bridgman preparation method thereof. The chemical formula of the cerium-doped rare earth borate scintillating crystal is Li6Gd1-x-yYxCey(BO3)3, wherein the numeric range of x is from 0 to 0.9999, and the numeric range of y is from 0.0001 to 0.1. In the cerium-doped rare earth borate scintillating crystal of the invention, by partially replacing a Gd element with an element Y with approximate electronegativity and relatively smaller atomic number, the detection property of the gadolinium lithium borate crystal on neutrons is optimized and the raw material cost of crystal preparation is reduced. The Bridgman preparation method has the characteristics of simple processing equipment, low energy consumption, high production efficiency, low cost and the like, is convenient to operate and can realize industrial production.
Description
Technical field
The present invention relates to field of crystals, be specifically related to rare earth doped borate scintillation crystal of a kind of cerium and falling crucible method preparation method thereof.
Background technology
Neutron is a kind of almost uncharged ultimate particle, it have penetration power strong, can discern light element particularly element such as hydrogen and lithium, differentiate neighbour's element, realize that isotropic substance replaces, surveys magnetic moment of atom, measures the distinct advantages such as dynamics of material internal.Thereby by neutron is carried out effectively and exactly surveying monitoring and the research that can realize to reactor nuclear chain reaction process, be militaryly go up necessary means that position that nuclear warhead is between ourselves and the enemy existed and quantity checks and survey, be to realize important weapon that effective detection of low density things concealeds such as explosive and drugs is carried out anti-terrorism, cracked down on smuggling and struggle against with traffic in drugs, in addition, neutron in subjects such as materialogy, physics, can provide the microscopic information of relevant material structure and dynamic foundation as probe.
Neutron source is the large-scale technology platform of neutron technology integrated application and research, in order to set up neutron source of future generation, requires to develop a new generation and has high-level efficiency, the neutron detector of position sensing.And neutron detection possesses over-all propertieies such as short, high light output fall time and high energy resolution, high α/β ratio, specific refractory power are little, highly anti-radiation hardness with material require.
In order to distinguish gamma-rays background signal in the detector, obtain the best effect of distinguishing, require material to have low gamma-rays susceptibility (Atom of Elements is little), high neutron response cross section σ.
Table 1.Li
6Gd (BO
3)
3: the contrast of Ce and traditional inorganic neutron detection material scintillation properties
Li
6Gd (BO
3)
3Crystal has very high detection efficiency to neutron
66 times of Li glass).Referring to table 1, doped Ce
3+Behind the ion, the spectral response coupling that this crystalline material has fast decay (28ns), emission wavelength (center is 385nm) and a photomultiplier (PMT) better, effective atomic number low (46.3), eliminate advantage such as gamma-rays background easily.Therefore, Li
6Gd (BO
3)
3: the discovery of Ce crystalline material and in the application prospect in neutron detection field, caused people's extensive concern, its crystal growth and performance study have become a new focus in neutron detection material field.
Up to now, disclosed domestic and foreign literature comprises patent, following characteristics is arranged with not enough:
1., on component, be Li
6Gd (BO
3)
3: Ce.Because Li
6Gd (BO
3)
3: the absorption cross of Gd ion pair neutron is excessive among the Ce, influenced to neutron response the most the sensitive lithium (
6Li) and boron (
11B), thereby reduced the examination ability of crystal to neutron to the absorption of neutron; The ordination number of Gd is big, to the gamma-rays sensitivity, is unfavorable for the detection of neutron signal; For the detection efficiency that improves neutron need be with the isotropic substance of Gd
155,157Gd separates, and this complex process, cost are very high.
2., on the crystal preparation method, all adopt crystal pulling method (top-seeded solution growth) or the zone melting method Li that grows
6Gd (BO
3)
3: the Ce crystal.The essential characteristic of crystal pulling method is in crystal furnace, by middle and high frequency or resistive heating, is melted in the Li in the platinum crucible
6Gd (BO
3)
3: the Ce raw material again through operations such as inoculation, growths, obtains the Li of certain orientation and certain size
6Gd (BO
3)
3: the Ce crystal.But, because near the thermograde the solid-liquid interface is bigger in the lifting furnace, adding the anisotropy of the thermal expansivity of crystal own, the crystal of growth is easy to cracking; When adopting this crystal of Czochralski grown, crystal is easy to the concave surface growth and makes crystal growing process interrupt; In the middle of the Czochralski grown process, crucible opens wide, B in the raw material
2O
3Volatilization bath component is departed from; The high viscosity of melt causes the nucleation difficulty; Heat transfer and transport of substances are slow, have determined its growth velocity extremely slow; Feed composition Li
2O, B
2O
3And Gd
2O
3Density variation very big, be easy to cause the melt layering.Problems such as the zone melting method crystal growth then exists growth conditions to be difficult to control, the thermograde macrocrystal is easy to crack, crystalline size that grow is little, of poor quality.
But the existence of the problems referred to above makes crystal pulling method and zone melting method be difficult to obtain the Li of large size, high quality practical application
6Gd (BO
3)
3: the Ce crystal; And, no matter be crystal pulling method or zone melting method, every crystal growing furnace crystal of once can only growing, efficient is lower, cost is high, is difficult to realize Li
6Gd (BO
3)
3: Ce crystalline suitability for industrialized production.
3., at luminescence center ion Ce
3+Doping way on, all by mixing CeO when the preparation of raw material
2(Ce
4+), and obtain by the mode of solid state reaction.This method exists solid state reaction to be difficult to thoroughly, easy residual Ce
4+And and then quencher Ce
3+Luminous possibility.
Summary of the invention
The objective of the invention is to overcome the deficiencies in the prior art, rare earth doped borate scintillation crystal of a kind of cerium and falling crucible method preparation method thereof are provided.
The present invention adopts following technical scheme to solve aforementioned technical problem:
The rare earth doped borate scintillation crystal of a kind of cerium, the host crystal of described scintillation crystal are boric acid gadolinium yttrium crystalline lithium, lithium gadolinium borate crystal or yttrium borate crystalline lithium, and the chemical formula of the rare earth doped borate scintillation crystal of described cerium is:
Li
6Gd
1-x-yY
xCe
y(BO
3)
3Wherein the span of x is 0～0.9999, is preferably 0.005～0.995; The span of y is 0.0001～0.1, is preferably 0.001～0.05, and satisfies x+y≤1.In the above-mentioned chemical formula, the digitized representation mol ratio in every kind of element lower right corner.
The preparation method of the rare earth doped borate scintillation crystal of cerium of the present invention comprises the steps:
1) joining of crystal growth raw material gets: mixing behind the various raw materials of weighing in proportion becomes admixtion;
2) polycrystal raw material is synthetic: admixtion is pressed into behind the material piece presintering makes Li in neutral atmosphere
6Gd
1-x-yY
xCe
y(BO
3)
3Polycrystal raw material;
3) crystal preparation: polycrystal raw material and seed crystal are put into crucible and close crucible, then crucible is placed crystal furnace, be higher than Li
6Gd
1-x-yY
xCe
y(BO
3)
3The temperature range of 40～120 ℃ of fusing points in raw material and seed crystal top in the fusion crucible, by Bridgman-Stockbarge method for growing Li
6Gd
1-x-yY
xCe
y(BO
3)
3Crystal, in the process of growth, the temperature of growth interface is 10-60 ℃/cm, dropping speed of the crucible is less than 4mm/h.
Preferable, the raw material in the described step 1) comprises: contain B element raw material, contain Gd element raw material, contain the Y element raw material, contain Ce element raw material and contain Li element raw material.
Preferably, the described B of containing element raw material is selected from H
3BO
3, B
2O
3Or the two mixture; Containing Gd element raw material is Gd
2O
3Containing the Y element raw material is Y
2O
3Contain Ce element raw material and be selected from CeO
2Or contain cerous compound, as Ce (NO
3)
3, CeF
3And composition thereof, more preferably contain cerous compound; Contain Li element raw material and be selected from Li
2CO
3, LiOH or Li
2O, the mixture that also can use mixture any two kinds in these three kinds of materials or these three kinds of materials simultaneously is as containing Li element raw material.
Preferably, the purity of described raw material is more than 99.99%.
Preferable, described step 2) admixtion in depresses to the material piece in the pressure conditions of 〉=5MPa.
Preferable, described step 2) the neutral atmosphere gas in (chemical property torpescence---not only be not easy to obtain electronics but also be difficult for losing the gas of electronics) is gases such as high-purity argon gas or high pure nitrogen.
The temperature of the presintering preferable, described step 2) is 610-710 ℃, and the time of presintering is more than the 1h, more preferably 10～20h.
Preferable, the seed crystal in the described step 3) is Li
6Gd
1-x-yY
xCe
y(BO
3)
3Crystal is oriented to ⊥ (001) direction.
Preferable, the material of crucible is a kind of in platinum, iridium, ruthenium or the rhodium in the described step 3), and crucible is one or more layers, and every layer thickness is 0.05-0.30mm.
Preferable, the mode of the close crucible in the described step 3) is the welding gun sealing, can prevent that component from volatilizing when high-temperature fusion.
Preferable, Li in the described step 3)
6Gd
1-x-yY
xCe
y(BO
3)
3Fusing point because the difference (difference of x, y value) of component and difference, its scope is 848～880 ℃.Those skilled in the art can determine different components crystalline fusing point according to differential thermal analysis.
Preferable, the dropping speed of the crucible in the described step 3) is 0.02～4mm/h.
Preferable, the crystal furnace in the described step 3) is the Bridgman crystal growing furnace.
In the described step 3), what those skilled in the art can be according to crystal shape and dimensional requirement is different, lays many crucibles in crystal furnace, the Li of the different shapes of growing simultaneously, different size
6Gd
1-x-yY
xCe
y(BO
3)
3Crystal, i.e. crucible shape (as multiple shapes such as cylindrical, rectangle or hexagons), controllable number.
Preferable, in the described step 3), after crystal growth finishes, reduce to room temperature through the time more than 10 hours, further preferred rate of temperature fall is 10～90 ℃/h, and crystalline size is big more, and rate of temperature fall is more little.
Preferable, in the described step 3), also need the Li that descent method for growing is obtained
6Gd
1-x-yY
xCe
y(BO
3)
3The crystal aftertreatment of annealing.
The concrete steps of described annealing aftertreatment are: crystal is placed the equally distributed crystal furnace of temperature, under the protection of neutral atmosphere, be warming up to 600～800 ℃, and be incubated in this temperature range, slowly reduce to room temperature after the insulation.The purpose of this annealing aftertreatment is to eliminate residual thermal stresses in the crystal body, thereby avoids crystal to cause crystal cleavage by stress man-hour adding.
Preferably, neutral atmosphere is selected from nitrogen or argon gas described in the annealing aftertreatment technology.
Preferably, temperature rise rate and rate of temperature fall described in the annealing aftertreatment technology are all less than 100 ℃/h, and further preferred temperature rise rate is 40～80 ℃/h, and rate of temperature fall is 20～40 ℃/h, and crystalline size is big more, and warming and cooling rate is more little.
Preferable, soaking time is preferably 5～24h greater than 5h described in the annealing aftertreatment technology.
The invention provides the rare earth doped borate scintillation crystal of a kind of cerium, this scintillation crystal compared with prior art, on component, pass through close with electronegativity and ionic radius, and the littler relatively element Y of ordination number comes part to replace the Gd element, thereby optimized the detection performance of lithium gadolinium borate crystal, and reduced the cost of preparation crystal desired raw material for neutron; Simultaneously, the borate doped gadolinium yttrium of cerium of the present invention lithium scintillation crystal is at luminescence center ion Ce
3+Doping way on, contain cerous compound by mixing in the composition of raw materials, improved in the crystal effectively luminescence center ion Ce
3+Content, improved Li
6Gd
1-x-yY
xCe
y(BO
3)
3The crystalline luminous intensity.
The present invention also provides the improved crucible descending system Preparation Method of the borate doped gadolinium yttrium of a kind of this cerium lithium scintillation crystal, and this method comprises, is that initial feed more than 99.99% is according to Li with purity
6Gd
1-x-yY
xCe
y(BO
3)
3Chemical formula batching, uniform mixing and synthetic through high temperature, seed crystal with certain orientation is put into platinum crucible, platinum crucible and support system thereof are placed the decline stove, melt raw material and seed crystal top, by controlling furnace temperature, regulating temperature gradient of solid-liquid interface and select suitable processing parameters such as dropping speed of the crucible to realize the crystalline stable growth, can obtain complete transparent high quality Li
6Gd
1-x-yY
xCe
y(BO
3)
3Crystal (x=0～0.9999, y=0.0001～0.1) (as shown in figures 1 and 3).
Preparation method of the present invention has following outstanding feature:
1, under the airtight condition of crucible, carries out crystal growth: after polycrystal is inserted platinum crucible, with crucible top sealing in addition fully, platinum crucible can seal up the steam on melt top reliably, its bath component volatilization loss can not occur, in whole crystal growing process, avoided overflowing of boron oxide steam, it is invariable that bath composition can keep, almost all melt all can be grown to transparent crystals, helps to reduce the solid inclusion that generates in crystal owing to bath component nonstoichiometry proportioning;
2, the preferred crystal direction of growth and suitably reduce the thermograde of solid-liquid interface: method of the present invention adopts the seed crystal that is oriented to ⊥ (001) direction, and temperature gradient of solid-liquid interface is controlled in the scope of 10-60 ℃/cm, can effectively avoid lithium gadolinium borate crystal in process of growth, to ftracture.
Preparation method of the present invention and top-seeded solution growth (Czochralski method, crystal pulling method) and zone melting method (zone melting) compare, its advantage is: the temperature field is stable, component is not volatile, the yield rate height, the crystalline size of growth and profile can be controlled, and little thermograde makes crystal not easy to crack, efficiently solve the technical barrier (as shown in Figure 1 and Figure 2) of bath composition volatilization and crystal cleavage, realize the stable growth of high quality large size boric acid gadolinium yttrium crystalline lithium.In addition, this method processing unit is simple, easy to operate, and energy consumption is low, and growth efficiency height, cost hang down can realize suitability for industrialized production.
Description of drawings
The Li of Fig. 1 for adopting descent method for growing to make among the embodiment 1
6Gd
0.995Ce
0.005(BO
3) crystal.
The Li of Fig. 2 for adopting Czochralski grown to make
6Gd
0.995Ce
0.005(BO
3) crystal.
The Li of Fig. 3 for making among the embodiment 1
6Gd
0.995Ce
0.005(BO
3) rocking curve of crystal (010) face.
Fig. 4 is the Li of the different concns Y of descent method preparation
6Gd
1-x-0.03Y
xCe
0.03(BO
3)
3Crystal measured excitation of X-rays emmission spectrum under the same test condition.
Fig. 5 is for the cerium ion-doped concentration identical (0.5at%) of descent method preparation but the different Li of doping way
6Gd
0.995Ce
0.005(BO
3)
3Crystal prototype measured fluorescence spectrum under the same test condition.
Fig. 6 is for the cerium ion-doped concentration identical (0.5at%) of descent method preparation but the different Li of doping way
6Gd
0.995Ce
0.005(BO
3)
3Crystal prototype measured excitation of X-rays emmission spectrum under the same test condition.
Embodiment
Further describe rare earth doped borate scintillation crystal of cerium of the present invention and preparation method thereof below by specific embodiment.Should be understood that these embodiment only are used to the present invention is described but not limit the scope of the invention.
Embodiment 1
1, Li
6Gd
0.995Ce
0.005(BO
3)
3The crystalline preparation, concrete preparation method is as follows:
Initial feed consists of: be 99.99% high pure raw material Li with purity
2CO
3, Gd
2O
3, H
3BO
3And CeO
2Press Li
6Gd
0.995Ce
0.005(BO
3)
3The accurate weighing of stoichiometric ratio, mixing, under the pressure of 10MPa, it is pressed into φ 32 * 40mm
3The material piece, with the presintering 10 hours under 650 ℃ temperature of this material piece, obtain Li by solid state reaction
6Gd
0.995Ce
0.005(BO
3)
3Polycrystal;
By thickness be the individual layer platinum sheet of 0.15mm to make the maximum open diameter be φ 35mm, length overall is the taper crucible of 250mm;
⊥ (001) direction is of a size of φ 8 * 20mm
3Lithium gadolinium borate crystal as seed crystal;
Seed crystal is equipped with in the bottom, and be equipped with through the complete sealing of platinum crucible of abundant sintering lithium gadolinium borate polycrystal piece, airtight on top, and the crucible alumina-ceramic of packing into is drawn pipe down.
With 70 ℃/hour speed furnace temperature is risen to 890 ℃, is incubated 5 hours, slowly promote again and draw pipe down, treat the fusing of whole raw materials and seed crystal top after, be incubated 2 hours again, descend with 3mm/ hour speed then and draw pipe down.
Behind the growth ending, stop to descend drawing down and manage.Cooling process is set,, the temperature of crystal growing furnace is reduced to room temperature through 20 hours.Cut off the electricity supply, take out platinum crucible, the crystal in the crucible is stripped out.
Crystal places the equally distributed stove of temperature, and nitrogen atmosphere protection rises to 800 ℃ with 60 ℃/hour speed with furnace temperature down, is incubated 24 hours, is cooled to room temperature with 25 ℃/hour speed again, and such crystal can be processed into finished product.
A stove 8 lithium gadolinium borate crystals of can growing in the present embodiment.
2, Li
6Gd
0.995Ce
0.005(BO
3)
3Crystalline character detects:
Present embodiment uses descent method for growing boric acid gadolinium yttrium crystalline lithium.The bath component volatilization can be suppressed by close crucible, thereby the generation of solid inclusion in the crystal can be reduced; Carry out the crystalline oriented growth by the thermograde at suitable reduction solid-liquid interface place, the crystallographic orientation of preferred seed crystal, can overcome the cracking problem in the crystal growing process, thereby grow the crystal of large-size high-quality.The Li that Fig. 1 makes for the descent method for growing that adopts present embodiment
6Gd
0.995Ce
0.005(BO
3)
3Crystal, the Li of Fig. 2 for adopting Czochralski grown of the prior art to make
6Gd
0.995Ce
0.005(BO
3)
3Crystal is compared as can be known by Fig. 1 and Fig. 2, and the preparation method of present embodiment can overcome the cracking problem in the crystal growing process, and the crystalline size that growth makes is big, complete and not easy to crack.The Li of Fig. 3 for making in the present embodiment
6Gd
0.995Ce
0.005(BO
3)
3The rocking curve of crystal (010) face, the result shows that the high width of the half-peak of crystal rocking curve is narrow, and this shows that crystalline monocrystalline degree is very high, and quality is good.
Crucible by choosing different shape, the number of adjusting crucible in the crystal growing furnace can be realized the mass growth of different shape crystal (taper crystal as shown in Figure 1 etc.).Fig. 4 is the Li of the different concns Y of descent method preparation
6Gd
1-x-0.03Y
xCe
0.03(BO
3)
3(cerium ion in the crystal is all by doped Ce O for crystal
2Mode introduce) measured excitation of X-rays emmission spectrum (x=0,0.1,0.3) under the same test condition regulate owing on crystal composition, carry out component by the mode of taking Y partly to replace Gd, constant substantially by luminous as can be seen peak position among Fig. 4.
Fig. 5 is the Li of the different cerium ion-doped modes of descent method preparation
6Gd
0.995Ce
0.005(BO
3)
3Crystal measured fluorescence spectrum under the same test condition.Fig. 6 is the Li of the different cerium ion-doped modes of descent method preparation
6Gd
0.995Ce
0.005(BO
3)
3Crystal measured excitation of X-rays emmission spectrum under the same test condition.By among Fig. 5 and Fig. 6 as can be seen: the compound of taking to contain trivalent cerium ion on the doping way of luminescence center ion Ce is prepared burden as initial feed, has increased the crystalline luminous intensity.
Embodiment 2
With purity 99.99% LiOH, Gd
2O
3, Y
2O
3, Ce (NO
3)
3And B
2O
3For initial feed is pressed Li
6Gd
0.7Y
0.295Ce
0.005(BO
3)
3The accurate weighing of stoichiometric ratio, mixing, under the pressure of 15MPa, it is pressed into φ 32 * 40mm
3The material piece, with the presintering 15 hours under 700 ℃ temperature of this material piece, obtain Li by solid state reaction
6Gd
0.7Y
0.295Ce
0.005(BO
3)
3Polycrystal.
The control furnace temperature is 930 ℃, and lowering speed is 1.5mm/ hour, and all the other press example 1 described processing condition, can grow 6 Li
6Gd
0.7Y
0.295Ce
0.005(BO
3)
3Crystal.
With purity 99.99% high pure raw material Li
2CO
3, Y
2O
3, Ce (NO
3)
3And H
3BO
3Press Li
6Y
0.995Ce
0.005(BO
3)
3The accurate weighing of stoichiometric ratio, mixing, under the pressure of 10MPa, it is pressed into φ 32 * 40mm
3The material piece, with the presintering 12 hours under 710 ℃ temperature of this material piece, obtain Li by solid state reaction
6Y
0.995Ce
0.005(BO
3)
3Polycrystal.
The control furnace temperature is 950 ℃, and lowering speed is for being 2.7mm/ hour, and all the other press example 1 described processing condition, can grow 10 Li
6Y
0.995Ce
0.005(BO
3)
3Crystal.
Embodiment 4
With purity 99.99% high pure raw material Li
2O, Li
2CO
3, Gd
2O
3, Y
2O
3, Ce (NO
3)
3, CeO
2, H
3BO
3And B
2O
3Press Li
6Gd
0.895Y
0.005Ce
0.1(BO
3)
3The accurate weighing of stoichiometric ratio, mixing, under the pressure of 10MPa, it is pressed into φ 32 * 40mm
3The material piece, with the presintering 12 hours under 710 ℃ temperature of this material piece, obtain Li by solid state reaction
6Gd
0.895Y
0.005Ce
0.1(BO
3)
3Polycrystal.
The control furnace temperature is 950 ℃, and lowering speed is for being 2.7mm/ hour, and all the other press example 1 described processing condition, can grow 10 Li
6Gd
0.895Y
0.005Ce
0.1(BO
3)
3Crystal.
Embodiment 5
With purity 99.99% high pure raw material Li
2O, LiOH, Gd
2O
3, Y
2O
3, CeF
3, CeO
2And H
3BO
3Press Li
6Gd
0.0049Y
0.995Ce
0.0001(BO
3)
3The accurate weighing of stoichiometric ratio, mixing, under the pressure of 10MPa, it is pressed into φ 32 * 40mm
3The material piece, with the presintering 12 hours under 710 ℃ temperature of this material piece, obtain Li by solid state reaction
6Gd
0.0049Y
0.995Ce
0.0001(BO
3)
3Polycrystal.
The control furnace temperature is 950 ℃, and lowering speed is for being 2.7mm/ hour, and all the other press example 1 described processing condition, can grow 10 Li
6Gd
0.0049Y
0.995Ce
0.0001(BO
3)
3Crystal.
Embodiment 6
With purity 99.99% high pure raw material Li
2O, LiOH, Li
2CO
3, Gd
2O
3, Y
2O
3, Ce (NO
3)
3, CeF
3, CeO
2, H
3BO
3And B
2O
3Press Li
6Gd
0.7Y
0.25Ce
0.05(BO
3)
3The accurate weighing of stoichiometric ratio, mixing, under the pressure of 10MPa, it is pressed into φ 32 * 40mm
3The material piece, with the presintering 12 hours under 710 ℃ temperature of this material piece, obtain Li by solid state reaction
6Gd
0.7Y
0.25Ce
0.05(BO
3)
3Polycrystal.
The control furnace temperature is 950 ℃, and lowering speed is for being 2.7mm/ hour, and all the other press example 1 described processing condition, can grow 10 Li
6Gd
0.7Y
0.25Ce
0.05(BO
3)
3Crystal.
Embodiment 7
With purity 99.99% high pure raw material Li
2CO
3, Gd
2O
3, Y
2O
3, Ce (NO
3)
3) and H
3BO
3Press Li
6Gd
0.75Y
0.245Ce
0.005(BO
3)
3The accurate weighing of stoichiometric ratio, mixing, under the pressure of 10MPa, it is pressed into φ 32 * 40mm
3The material piece, with the presintering 12 hours under 710 ℃ temperature of this material piece, obtain Li by solid state reaction
6Gd
0.75Y
0.245Ce
0.005(BO
3)
3Polycrystal.
The control furnace temperature is 950 ℃, and lowering speed is for being 2.7mm/ hour, and all the other press example 1 described processing condition, can grow 10 Li
6Gd
0.75Y
0.245Ce
0.005(BO
3)
3Crystal.
Embodiment 8
With purity 99.99% high pure raw material Li
2CO
3, Gd
2O
3, Y
2O
3, and H
3BO
3Press Li
6Y
0.9999Ce
0.0001(BO
3)
3The accurate weighing of stoichiometric ratio, mixing, under the pressure of 10MPa, it is pressed into φ 32 * 40mm
3The material piece, with the presintering 12 hours under 710 ℃ temperature of this material piece, obtain Li by solid state reaction
6Y
0.9999Ce
0.0001(BO
3)
3Polycrystal.
The control furnace temperature is 950 ℃, and lowering speed is for being 2.7mm/ hour, and all the other press example 1 described processing condition, can grow 10 Li
6Y
0.9999Ce
0.0001(BO
3)
3Crystal.
Claims (11)
1. rare earth doped borate scintillation crystal of cerium, the host crystal of described scintillation crystal is boric acid gadolinium yttrium crystalline lithium, lithium gadolinium borate crystal or yttrium borate crystalline lithium, and the chemical formula of the rare earth doped borate scintillation crystal of described cerium is:
Li
6Gd
1-x-yY
xCe
y(BO
3)
3, wherein the span of x is 0～0.9999, the span of y is 0.0001～0.1, and satisfies x+y≤1.
2. the rare earth doped borate scintillation crystal of cerium described in claim 1 is characterized in that the span of described x is 0.005～0.995, and the span of y is 0.001～0.05.
3. the preparation method of the rare earth doped borate scintillation crystal of the described cerium of arbitrary claim in the claim 1 or 2 comprises the steps:
1) joining of crystal growth raw material gets: mixing behind the various raw materials of weighing in proportion becomes admixtion;
2) polycrystal raw material is synthetic: admixtion is pressed into behind the material piece presintering makes Li in neutral atmosphere
6Gd
1-x-yY
xCe
y(BO
3)
3Polycrystal raw material;
3) crystal preparation: polycrystal raw material and seed crystal are put into crucible and close crucible, then crucible is placed crystal furnace, be higher than Li
6Gd
1-x-yY
xCe
y(BO
3)
3Interior raw material of fusion crucible and seed crystal top in the temperature range that fusing point is 40～120 ℃ are by the Bridgman-Stockbarge method for growing crystal.
4. the preparation method of the rare earth doped borate scintillation crystal of the cerium described in claim 3 is characterized in that, the raw material in the described step 1) comprises: contain B element raw material, contain Gd element raw material, contain the Y element raw material, contain Ce element raw material and contain Li element raw material.
5. the preparation method of the rare earth doped borate scintillation crystal of the cerium described in claim 4 is characterized in that, the described B of containing element raw material is selected from H
3BO
3Or B
2O
3Containing Gd element raw material is Gd
2O
3Containing the Y element raw material is Y
2O
3Contain Ce element raw material and be selected from CeO
2, Ce (NO
3)
3Or CeF
3Contain Li element raw material and be selected from Li
2CO
3, LiOH or Li
2O.
6. the preparation method of the rare earth doped borate scintillation crystal of the cerium described in claim 3 is characterized in that, in the crystal growing process in the described step 3), the temperature of growth interface is 10-60 ℃/cm, and dropping speed of the crucible is 0.02-4mm/h.
7. the preparation method of the rare earth doped borate scintillation crystal of the cerium described in claim 3 is characterized in that, described step 2) in the temperature of presintering be 610-710 ℃, the time of presintering is greater than 1h.
8. the preparation method of the rare earth doped borate scintillation crystal of the cerium described in claim 3; it is characterized in that; in the described step 3); also need the crystal that descent method for growing the obtains aftertreatment of annealing; and the concrete steps of described annealing aftertreatment are: crystal is placed the equally distributed crystal furnace of temperature, under the protection of neutral atmosphere, be warming up to 600～800 ℃; and in this temperature range, be incubated, reduce to room temperature after the insulation.
9. the preparation method of the rare earth doped borate scintillation crystal of the cerium described in claim 8 is characterized in that, described temperature rise rate is 40～80 ℃/h, and rate of temperature fall is 20～40 ℃/h.
10. the preparation method of the rare earth doped borate scintillation crystal of the cerium described in claim 3 is characterized in that, the material of the crucible in the described step 3) is a kind of in platinum, iridium, ruthenium or the rhodium, and crucible is one or more layers, and every layer thickness is 0.05～0.30mm.
11. the rare earth doped borate scintillation crystal of the described cerium of arbitrary claim is in the application in neutron detection field in claim 1 or 2.
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