CN101597796A - The growing method of lithium gadolinium borate crystal - Google Patents
The growing method of lithium gadolinium borate crystal Download PDFInfo
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- CN101597796A CN101597796A CNA2009100542127A CN200910054212A CN101597796A CN 101597796 A CN101597796 A CN 101597796A CN A2009100542127 A CNA2009100542127 A CN A2009100542127A CN 200910054212 A CN200910054212 A CN 200910054212A CN 101597796 A CN101597796 A CN 101597796A
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- gadolinium borate
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Abstract
The invention discloses a kind of growing method of lithium gadolinium borate crystal, relate to field of crystal growth.This method is that the crystal growth raw material is adopted Czochralski grown, and wherein, the chemical formula of described lithium gadolinium borate crystal is Li
6Ce
xGd
1-xB
3O
9, the span of x is 0＜x≤0.1; When adopting Czochralski grown, selecting lower part for use is that the special-shaped crucible of arc or conical lower portion is as growth crucible.The present invention has overcome the Czochralski grown lithium gadolinium borate crystal that uses common round tube type crucible and has been prone to recessed interface or is difficult to grow up to large diameter shortcoming by using special-shaped crucible and post heating device.The crystal that grows with this method has that size is big, the optical quality advantages of higher, can be used for neutron detection, can also be used to surveying α, β, gamma-rays etc.
Description
Technical field
The present invention relates to field of crystal growth, be specifically related to a kind of growing method of lithium gadolinium borate crystal.
Background technology
(molecular formula consists of Li to lithium gadolinium borate crystal
6Ce
xGd
1-xB
3O
9) lithium-6 by enrichment in the crystal or boron-10 or gadolinium-155 or gadolinium-157 isotropic substance and neutron react detected neutron, at first the J.B.Czirr by the U.S. reported its potential use as the neutron detection scintillation crystal in 1996.As a kind of novel neutron detection scintillation crystal, Li
6Ce
xGd
1-xB
3O
9Have the following advantages:
(1) contains three kinds of isotopic elements that neutron had big capture cross-section of Li, B and Gd simultaneously, can select different isotopic enrichment combinations according to different detection demands, optimization design goes out the crystal composition of higher detection efficiency, so this crystal has very strong adaptability.
(2) luminescence center is Ce
3+Ion, having fall time short (28ns), light output, high (each neutron excites and produces 40000 photoelectrons, every MeV gamma-rays excites and produces 25000 photoelectrons) and emission wavelength (centre wavelength is 395nm) and characteristics such as photomultiplier (PMT) coupling is good, thereby its detection efficiency height, be
66 times and 9 times of BC-454 of Li glass.
(3) effective atomic number low (46.3) is eliminated the gamma-rays background easily.
(4) specific refractory power low (1.67@405nm) is easy to polymkeric substance compoundly, is very suitable for big area neutron detection and imaging.
(5) both can utilize this crystalline bulk-shaped monocrystal to make the neutron detector of small area, and also can utilize the specific particulate powder of this crystalline to produce the big area neutron detector.
Crystal pulling method claims Czoncharlski method again, is caochralski (J.Czochralski) in the method for pulling growth high quality single crystal from melt of invention in 1917.This method important crystalline materials such as neodymium-doped yttrium pyralspite, vanadic acid yttrium, Lithium niobium trioxide and silicon single crystal of can growing.
Lithium gadolinium borate crystal fusing point low (about 860 ℃) is fit to use Czochralski grown.But this crystal has shortcomings such as melt viscosity is big, crystalline growth velocity slow, crystal poor thermal conductivity simultaneously, make this crystal in the Czochralski grown process, very easily form supercooled state or interface inversion, thereby make that this crystal diameter is difficult to amplify, even causing growth to be forced to end, this is the greatest problem that runs in the growth.The general Czochralski grown lithium gadolinium borate crystal that uses common round tube type crucible is prone to recessed interface or is difficult to grow up to large diameter shortcoming in the prior art when using this crucible to come growing crystal.Therefore, be necessary further to improve in that existing Czochralski grown is technical, to grow the large-size high-quality lithium gadolinium borate crystal that satisfies application requiring.
The convection current situation of melt is analyzed when lithium gadolinium borate crystal is grown, find after the crystalline diameter increases to a certain degree, the forced convection of melt will transfer to the heat of crucible bottom the solid-liquid interface of crystal growth, make crystal growth centre temperature drift, cause crystal growth to carry out, even understand the crystal that corrode has been grown, thereby produce recessed interface, make the interface of crystal growth overturn, thereby crystal can't be grown up, limited the crystalline size.
Summary of the invention
The growing method that the purpose of this invention is to provide a kind of lithium gadolinium borate crystal, for the crystal growth raw material is adopted Czochralski grown, wherein, the chemical formula of described lithium gadolinium borate crystal is Li
6Ce
xGd
1-xB
3O
9, the span of x is 0＜x≤0.1; When adopting Czochralski grown, selecting upper part for use is the cylinder bodily form, and lower part is that the special-shaped crucible of arc or conical lower portion is as growth crucible.
Described crystal growth raw material is made by the method that comprises the following steps:
A. by mix behind the various raw materials of proportioning weighing;
B. the crystal growth raw material is synthetic.
Raw material in the described steps A comprises and contains Li element raw material, contains B element raw material, contains Gd element raw material and contain Ce element raw material.
Preferably, the described Li of containing element raw material is selected from Li
2CO
3With among the LiOH one or more; The described B of containing element raw material is selected from H
3BO
3And B
2O
3In one or more; The described Gd of containing element raw material is Gd
2O
3The described Ce of containing element raw material is selected from CeO
2And Ce (NO
3)
3In one or more.
Preferred, the weight of the described B of containing element raw material excessive 1～5% (that is: contain the weight excessive 1～5% that the weight ratio of B element raw material is calculated according to the stoichiometric ratio of B element in the chemical formula).
The synthesis step of the crystal growth raw material among the described step B is: the batching that will mix is pressed into the material piece, is warmed up to 440～460 ℃, and sintering was lowered the temperature after 9～11 hours; Take out the back and grind, be pressed into the material piece once more, be warming up to 650～750 ℃, sintering 9～11 hours.
The concrete steps of described Czochralski grown crystal are:
The crystal growth raw material of preparation is seated in the special-shaped crucible, puts into lifting furnace; Then seed crystal is contained on the seed rod, and seed rod is fixed on the lifting rod; Make seed crystal touch fused crystal growth raw material liquid level; Then by rotation, lift lifting rod and come growing crystal.
Preferably, when adopting Czochralski grown, crystal growth temperature is 800～865 ℃, and rotating speed is 1～10rpm during crystal growth, and pulling rate is 0.1～2mm/h, and rate of temperature fall is 0.4～0.8 ℃/h.
Preferably, when adopting Czochralski grown, crystal growth atmosphere is: air, nitrogen, argon gas, contain the nitrogen of oxygen 1～10at.% or contain the argon gas of oxygen 1～10at.%.
Preferably, when adopting Czochralski grown, crystal growth seed crystal is platinum wire or lithium gadolinium borate single crystal seed, and lithium gadolinium borate single crystal seed direction can be any.
Preferably, described special-shaped crucible is iraurite or platinum crucible; Interior diameter suitable for reading, height and the thickness of this abnormal shape crucible can be determined according to the crystalline size of required growth by those skilled in the art.
Preferably, described special-shaped mouth of pot also is provided with metal ring as post heating device, and the external diameter of described metal ring is identical with the interior diameter suitable for reading of matching used crucible, and thickness is identical with matching used sidewall of crucible thickness.
Czochralski grown method of the present invention can transfer to sidewall of crucible with the heat of crucible bottom by using special-shaped crucible, avoids its interface to crystal growth to produce directly influence, can grow the high-quality lithium gadolinium borate crystal of major diameter.Simultaneously, by using upper part diameter identical, lower part is the purpose that the crucible of arc or conical lower portion changes melt eddy current shape.Because the lithium gadolinium borate crystal heat conductivility is poor, in the Czochralski grown shouldering process, under the constant situation of thermograde, the shoulder area increases by law of indices in time, thereby causes crystal runaway condition to occur in the shouldering process in pulling rate and melt; Growth method of the present invention increases near the radial symmetry gradient of crystal growth interface by post heating device is set, and controls crystalline shouldering speed, thereby reaches the purpose of control growing state.The invention provides a kind of Czochralski grown technology that is specifically designed to the growth lithium gadolinium borate crystal, overcome the Czochralski grown lithium gadolinium borate crystal that uses common round tube type crucible and be prone to recessed interface or be difficult to grow up to large diameter shortcoming.The crystal that grows with this method has that size is big, the optical quality advantages of higher, can be used for neutron detection, can also be used to surveying α, β, gamma-rays etc., can realize that through engineering approaches uses.
Description of drawings
Fig. 1 the present invention used Iridium Crucible diagrammatic cross-section of lithium gadolinium borate crystal of growing.
Fig. 2 the present invention used platinum crucible diagrammatic cross-section of lithium gadolinium borate crystal of growing.
Embodiment
Further describe lithium gadolinium borate laser crystals of the present invention and preparation method thereof below by specific embodiment.Should be understood that these embodiment only to be used to the present invention is described and be not used in and limit the scope of the invention.
The Czochralski grown lithium gadolinium borate crystal that present embodiment uses, take special crucible shape and insulation measure, crystal be can overcome and in conventional Czochralski grown process, supercooled state or interface inversion very easily formed, thereby make that this crystal diameter is difficult to amplify, even the shortcoming that causes growing and be forced to end, thereby grow the high-quality crystal of major diameter.Specific embodiment is as follows:
Embodiment 1
According to consisting of Li
6Ce
0.01Gd
0.99B
3O
9Weighing Li
2CO
3(purity is 99.99%) 270g, Gd
2O
3(purity is 99.99%) 217.2g, H
3BO
3(99.99%) 228.6g and CeO
2(99.99%) 2.06g mixes, and being pressed into diameter is the cylindric bulk of 50mm, puts into the corundum cup, 450 ℃ of sintering temperatures 10 hours, takes out, and grinds again, is pressed into bulk again, inserts in the retort furnace, 700 ℃ of following sintering 10 hours.After the taking-up, put into special-shaped Iridium Crucible (sectional view as shown in Figure 1), with the lithium gadolinium borate monocrystalline is seed crystal, crystal growth temperature is 800 ℃, and rotating speed is 3rpm, and pulling rate is 0.5mm/h, rate of temperature fall is 0.8 ℃/h, through 80 hours growth, can grow diameter was 32mm, and length is the lithium gadolinium borate monocrystalline about 40mm.
Embodiment 2
According to consisting of Li
6Ce
0.01Gd
0.99B
3O
9Weighing Li
2CO
3(99.99%) 270g, Gd
2O
3(99.99%) 217.2g, H
3BO
3(99.99%) 237.7g and CeO
2(99.99%) 2.06g mixes, and being pressed into diameter is the cylindric bulk of 50mm, puts into the corundum cup, 440 ℃ of sintering temperatures 11 hours, takes out, and grinds again, is pressed into bulk again, inserts in the retort furnace, 750 ℃ of following sintering 9 hours.After the taking-up, put into special-shaped platinum crucible (sectional view as shown in Figure 2), the iraurite ring that it is 80mm that mouth of pot is placed internal diameter 45mm, an external diameter is a post heating device.To mix cerium lithium gadolinium borate monocrystalline is seed crystal, and crystal growth temperature is 865 ℃, and rotating speed is 10rpm, and pulling rate is 0.1mm/h, and rate of temperature fall is 0.4 ℃/h, and through 60 hours growth, can grow diameter was 40mm, and length is to mix cerium lithium gadolinium borate monocrystalline about 30mm.
Embodiment 3
According to consisting of Li
6Ce
0.1Gd
0.9B
3O
9Weighing LiOH (99.99%) 175.2g, Gd
2O
3(99.99%) 199.1g, B
2O
3(99.99%) 127.8g and Ce (NO
3)
3(99.99%) 39.8g mixes, and being pressed into diameter is the cylindric bulk of 50mm, puts into the corundum cup, 440 ℃ of sintering temperatures 11 hours, takes out, and grinds again, is pressed into bulk again, inserts in the retort furnace, 650 ℃ of following sintering 11 hours.After the taking-up, put into special-shaped platinum crucible (sectional view as shown in Figure 2), the iraurite ring that it is 80mm that mouth of pot is placed internal diameter 50mm, an external diameter is a post heating device.With the platinum wire is seed crystal, and crystal growth temperature is 865 ℃, and rotating speed is 10rpm, and pulling rate is 0.1mm/h, and rate of temperature fall is 0.4 ℃/h, and through 60 hours growth, can grow diameter was 41mm, and length is to mix cerium lithium gadolinium borate monocrystalline about 28mm.
Embodiment 4
According to consisting of Li
6Ce
0.1Gd
0.9B
3O
9Weighing LiOH (99.99%) 175.2g, Gd
2O
3(99.99%) 199.1g, B
2O
3(99.99%) 131.6 and Ce (NO
3)
3(99.99%) 39.8g mixes, and being pressed into diameter is the cylindric bulk of 50mm, puts into the corundum cup, 460 ℃ of sintering temperatures 9 hours, takes out, and grinds again, is pressed into bulk again, inserts in the retort furnace, 750 ℃ of following sintering 9 hours.After the taking-up, put into special-shaped platinum crucible (sectional view as shown in Figure 2), the iraurite ring that it is 80mm that mouth of pot is placed internal diameter 40mm, an external diameter is a post heating device.With the platinum wire is seed crystal, and crystal growth temperature is 865 ℃, and rotating speed is 1rpm, and pulling rate is 2mm/h, and rate of temperature fall is 0.8 ℃/h, and through 60 hours growth, can grow diameter was 35mm, and length is to mix cerium lithium gadolinium borate monocrystalline about 31mm.
Claims (10)
1, a kind of growing method of lithium gadolinium borate crystal, for the crystal growth raw material is adopted Czochralski grown, wherein, the chemical formula of described lithium gadolinium borate crystal is Li
6Ce
xGd
1-xB
3O
9, the span of x is 0＜x≤0.1; When adopting Czochralski grown, selecting upper part for use is the cylinder bodily form, and lower part is that the special-shaped crucible of arc or conical lower portion is as growth crucible.
2, the growing method of lithium gadolinium borate crystal according to claim 1 is characterized in that described crystal growth raw material is made by the method that comprises the following steps:
A. by mix behind the various raw materials of proportioning weighing;
B. the crystal growth raw material is synthetic.
3, as the growing method of lithium gadolinium borate crystal as described in the claim 2, it is characterized in that the raw material in the described steps A comprises and contains Li element raw material, contains B element raw material, contains Gd element raw material and contain Ce element raw material.
4, as the growing method of lithium gadolinium borate crystal as described in the claim 3, it is characterized in that the described Li of containing element raw material is selected from Li
2CO
3Or among the LiOH one or more; The described B of containing element raw material is selected from H
3BO
3Or B
2O
3In one or more; The described Gd of containing element raw material is Gd
2O
3The described Ce of containing element raw material is selected from CeO
2Or Ce (NO
3)
3In one or more.
5, as the growing method of lithium gadolinium borate crystal as described in the claim 3, it is characterized in that the described weight excessive 1～5% that contains B element raw material.
6, as the growing method of lithium gadolinium borate crystal as described in the claim 2, it is characterized in that the synthesis step of described crystal growth raw material is: the admixtion that mixes is pressed into the material piece, is warmed up to 440～460 ℃, sintering is after 9～11 hours, cooling; Take out the back and grind, be pressed into the material piece once more, be warming up to 650～750 ℃, sintering 9～11 hours.
7, the growing method of lithium gadolinium borate crystal according to claim 1 is characterized in that, when adopting Czochralski grown, crystal growth temperature is 800～865 ℃, rotating speed is 1～10rpm during crystal growth, and pulling rate is 0.1～2mm/h, and rate of temperature fall is 0.4～0.8 ℃/h.
8, the growing method of lithium gadolinium borate crystal according to claim 1 is characterized in that, when adopting Czochralski grown, crystal growth atmosphere is: air, nitrogen, argon gas, contain the nitrogen of oxygen 1～10at.% or contain the argon gas of oxygen 1～10at.%; Crystal growth seed crystal is platinum wire or lithium gadolinium borate single crystal seed.
9, the growing method of lithium gadolinium borate crystal according to claim 1 is characterized in that described special-shaped crucible is iraurite or platinum crucible.
10, the growing method of lithium gadolinium borate crystal according to claim 1 is characterized in that, described special-shaped mouth of pot is provided with iraurite or platinum metal ring as post heating device.
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| DE69904639T2 (en) * | 1998-10-14 | 2003-11-06 | Memc Electronic Materials, Inc. | METHOD FOR EXACTLY DRAWING A CRYSTAL |
| US20020124792A1 (en) * | 2001-01-09 | 2002-09-12 | Hariprasad Sreedharamurthy | Crystal puller and method for growing single crystal semiconductor material |
| JP2004315258A (en) * | 2003-04-14 | 2004-11-11 | Shin Etsu Handotai Co Ltd | Production method for single crystal |
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| CN105525348A (en) * | 2015-12-25 | 2016-04-27 | 青岛大学 | Flux technology growth apparatus and method of rare earth doped orthophosphate crystals |
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| 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 |
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