CN102021651B - 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 the 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 identify light element particularly the element such as hydrogen and lithium, differentiate neighbour's element, realize isotropic substance replacements, the particular advantages such as dynamics of Measurement atom magnetic moment, mensuration material internal.Thereby by neutron being carried out effectively and exactly surveying monitoring and the research that can realize reactor nuclear chain reaction process, be the military upper position that nuclear warhead is between ourselves and the enemy existed and the quantity necessary means that checks and survey, be to realize important weapon that effective detection of the 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 the 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 short, High Light Output and the over-all propertieies such as high energy resolution, high α/β ratio, specific refractory power are little, highly anti-radiation hardness fall time with material require.
In order to distinguish Gamma-ray Background At Balloon 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
| Title | Doping agent | Density (g/cm 3) | Number of photons/neutron | Number of photons/MeV (gamma-rays) | α/β leads | Peak luminous wavelength (nm) | Fall time (ns) |
| 6Li 6 depGd( 3) 3 | Ce | 3.5 | 40,000 | 25,000 | 0.32 | 385 | 28 |
| 6Li glass | Ce | 2.5 | 6,000 | 4,000 | 0.3 | 395 | 75 |
| 6LiI | Eu | 4.1 | 50,000 | 12,000 | 0.87 | 470 | 1400 |
| 6LiF/ZnS | Ag | 2.6 | 160,000 | 15,000 | 0.44 | 450 | 1000 |
| LiBaF 3 | Ce/K | 5.3 | 3,500 | 5,000 | 0.14 | 190/330 | 34/2100 |
| Cs 2LiYCl 6 | Ce | 3.31 | 70,000 | 22,000 | 0.66 | 376/404 | 3/1000 |
| LiYSiO 4 | Ce | 3.8 | 10,000 | 10,000 | 410 | 38 | |
| Li 2B 4O 7 | Ce/Cu | 2.44 | 500 | 0.3 | 340/370 | 1000 |
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, this crystalline material has that fast decay (28ns), emission wavelength (center is 385nm) are better with the Spectral response match of photomultiplier (PMT), effective atomic number is low (46.3), eliminate easily the advantage such as Gamma-ray Background At Balloon.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 of neutron detection Material Field.
Up to now, published 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 crosssection of Gd ion pair neutron is excessive among the Ce, affected the lithium the sensitiveest to neutron response (
6Li) and boron (
11B) to the absorption of neutron, thereby reduced the examination ability of crystal to neutron; The ordination number of Gd is large, and is responsive to gamma-rays, is unfavorable for the detection of neutron signal; For the detection efficiency that improves neutron need to 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 medium, 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 larger 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 also so that crystal growing process interrupts; 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 transmission and transport of substances are slow, have determined that its growth velocity is extremely slow; Feed composition Li
2O, B
2O
3And Gd
2O
3Density variation very large, be easy to cause the melt layering.The problems such as the growth of zone melting method crystal 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.
The existence of the problems referred to above is so that but crystal pulling method and zone melting method are 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: the suitability for industrialized production of Ce crystal.
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.The 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 object of the invention is to overcome the deficiencies in the prior art, the 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 melting 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.
Better, described step 1) raw material in 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, such 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 also can use the mixture of mixture any two kinds in these three kinds of materials or these three kinds of materials as containing Li element raw material simultaneously.
Preferably, the purity of described raw material is more than 99.99%.
Better, described step 2) admixtion in depresses to the material piece in the pressure conditions of 〉=5MPa.
Better, 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 the gases such as high-purity argon gas or high pure nitrogen.
The temperature of the presintering better, described step 2) is 610-710 ℃, and the time of presintering is more than the 1h, more preferably 10～20h.
Better, described step 3) seed crystal in is Li
6Gd
1-x-yY
xCe
y(BO
3)
3Crystal is oriented to ⊥ (001) direction.
Better, described step 3) material of crucible is a kind of in platinum, iridium, ruthenium or the rhodium in, and crucible is one or more layers, and every layer thickness is 0.05-0.30mm.
The mode of the close crucible better, described step 3) is the welding gun sealing, can prevent that component from volatilizing when high-temperature fusion.
Better, described step 3) middle Li
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 according to differential thermal analysis the fusing point of different components crystal.
Better, described step 3) dropping speed of the crucible in is 0.02～4mm/h.
Better, described step 3) crystal furnace in is the Bridgman crystal growing furnace.
Described step 3) in, 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, namely crucible shape (such as various shapes such as cylindrical, rectangle or hexagons), quantity are controlled.
Better, described step 3) in, after the crystal growth is complete, be down to room temperature through the time more than 10 hours, further preferred rate of temperature fall is 10～90 ℃/h, and crystalline size is larger, and rate of temperature fall is less.
Better, described step 3) in, 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 be down 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 larger, and warming and cooling rate is less.
Better, 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, pass through close with electronegativity and ionic radius in component, and the relatively less element Y of ordination number comes part to replace the Gd element, thereby optimized the detection performance of lithium gadolinium borate crystal for neutron, and reduced the cost of preparation crystal desired raw material; 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 luminous intensity of crystal.
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 the 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, evenly mix 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, adjusting temperature gradient of solid liquid and selecting the suitable processing parameters such as dropping speed of the crucible to realize the stable growth of crystal, 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, carrying out the crystal growth under the airtight condition of crucible: 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 cracking in process of growth.
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, yield rate is high, and 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, the method processing unit is simple, and is easy to operate, and energy consumption is low, and growth efficiency is high, cost is low can realize suitability for industrialized production.
Description of drawings
Fig. 1 is the Li that adopts 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.
Fig. 3 is the Li that makes 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 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 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 for explanation the present invention but not limit the scope of the invention.
Embodiment 1
1, Li
6Gd
0.995Ce
0.005(BO
3)
3The preparation of crystal, 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, overall length 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 lower pipe.
With 70 ℃/hour speed furnace temperature is risen to 890 ℃, be incubated 5 hours, slowly promote again and draw lower pipe, after whole raw materials and the fusing of seed crystal top, be incubated again 2 hours, then draw lower pipe with 3mm/ hour speed decline.
After growth finishes, stop to descend and draw lower pipe.Cooling process is set, through 20 hours, the temperature of crystal growing furnace is down to room temperature.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 is lower, with 60 ℃/hour speed furnace temperature is risen to 800 ℃, 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)
3The nature examination of crystal:
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 oriented growth of crystal by the thermograde at suitable reduction solid-liquid interface place, the crystallographic orientation of preferred seed crystal, can overcome the problem of Cracking 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 problem of Cracking in the crystal growing process, and the crystalline size that growth makes is large, complete and not easy to crack.Fig. 3 is the Li that makes in the present embodiment
6Gd
0.995Ce
0.005(BO
3)
3The rocking curve of crystal (010) face, the result shows that half peak height width of crystal rocking curve is narrow, and this monocrystalline degree that shows crystal 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 under the same test condition, 0.1,0.3), owing on crystal composition, carry out composition regulation by the mode of taking Y partly to replace Gd, by finding out among Fig. 4 that luminous peak position is substantially constant.
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 finding out among Fig. 5 and Fig. 6: 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 luminous intensity of crystal.
Embodiment 2
Be 99.99% LiOH, Gd with purity
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.
Embodiment 3
Be 99.99% high pure raw material Li with purity
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
Be 99.99% high pure raw material Li with purity
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
Be 99.99% high pure raw material Li with purity
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
Be 99.99% high pure raw material Li with purity
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
Be 99.99% high pure raw material Li with purity
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
Be 99.99% high pure raw material Li with purity
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 (5)
1. the preparation method of the 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 that the span of 0～0.9999, y is 0.0001～0.1, and satisfies x+y≤1; Described scintillation crystal is applied to the neutron detection field, and described preparation method comprises the steps:
1) joining of crystal growth raw material gets: weighing contains B element raw material, contains Gd element raw material, contains the Y element raw material in proportion, and mixing after containing Ce element raw material and containing Li element raw material 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, the temperature of presintering are 610-710 ℃, and the time of presintering is greater than 1h;
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 interior raw material of melting crucible and seed crystal top in the temperature range that fusing point is 40～120 ℃, by the Bridgman-Stockbarge method for growing crystal, the temperature of growth interface is 10-60 ℃/cm, dropping speed of the crucible is 0.02-4mm/h;
4) annealing aftertreatment: 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, be down to room temperature after the insulation.
2. the preparation method of the rare earth doped borate scintillation crystal of cerium as claimed in claim 1, it is characterized in that, the host crystal of described scintillation crystal is boric acid gadolinium yttrium crystalline lithium 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 that the span of 0.005～0.995, y is 0.001～0.05, and satisfies x+y≤1.
3. such as the preparation method of claim 1 or the rare earth doped borate scintillation crystal of the described cerium of 2 arbitrary claims, it 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.
4. such as the preparation method of claim 1 or the rare earth doped borate scintillation crystal of the described cerium of 2 arbitrary claims, it is characterized in that described temperature rise rate is 40～80 ℃/h, rate of temperature fall is 20～40 ℃/h.
5. such as the preparation method of claim 1 or the rare earth doped borate scintillation crystal of the described cerium of 2 arbitrary claims, it is characterized in that, the material of the crucible 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.
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| CN104372410A (en) * | 2014-11-17 | 2015-02-25 | 中国科学院上海硅酸盐研究所 | Cerium-doped rare earth borate scintillation crystal and preparation method thereof |
| CN104927844B (en) * | 2015-07-15 | 2016-08-17 | 中南大学 | A kind of borate scintillation material |
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| DE112020006232T5 (en) * | 2019-12-20 | 2022-10-06 | Canon Optron Inc. | ION-CONDUCTIVE SOLID STATE AND ALL SOLID STATE BATTERY |
| CN113215659A (en) * | 2020-01-21 | 2021-08-06 | 德州学院 | Rare earth borate crystal material and preparation method and application thereof |
| CN113930842A (en) * | 2021-10-14 | 2022-01-14 | 上海应用技术大学 | Preparation method of cerium-doped lithium lutetium borate crystal |
| CN114775053B (en) * | 2022-03-28 | 2023-12-26 | 山东大学 | Cerium-lithium double-doped cesium-zirconium chloride scintillation crystal, preparation thereof and application thereof in neutron/gamma ray double-detection |
| CN115367767B (en) * | 2022-08-05 | 2023-06-13 | 广东省科学院资源利用与稀土开发研究所 | Lithium sodium yttrium borate and cerium doped compound and crystal thereof, and preparation methods and application thereof |
| CN115367766B (en) * | 2022-08-05 | 2023-06-13 | 广东省科学院资源利用与稀土开发研究所 | Lithium sodium lutetium borate, rare earth doped compound and crystal thereof, and preparation method and application thereof |
| CN115233307A (en) * | 2022-08-11 | 2022-10-25 | 山东重山光电材料股份有限公司 | Growth method and application of boron 11-LBO crystal |
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