CN105714374B - The growth of low-cost rare earth scintillation crystal - Google Patents
The growth of low-cost rare earth scintillation crystal Download PDFInfo
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- CN105714374B CN105714374B CN201610115971.XA CN201610115971A CN105714374B CN 105714374 B CN105714374 B CN 105714374B CN 201610115971 A CN201610115971 A CN 201610115971A CN 105714374 B CN105714374 B CN 105714374B
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- 239000013078 crystal Substances 0.000 title claims abstract description 226
- 230000012010 growth Effects 0.000 title claims abstract description 180
- 229910052761 rare earth metal Inorganic materials 0.000 title claims abstract description 88
- 150000002910 rare earth metals Chemical class 0.000 title claims abstract description 76
- 238000000034 method Methods 0.000 claims abstract description 75
- 239000002994 raw material Substances 0.000 claims abstract description 72
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 43
- 239000000463 material Substances 0.000 claims abstract description 43
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 23
- 229910052684 Cerium Inorganic materials 0.000 claims abstract description 22
- 230000001681 protective effect Effects 0.000 claims abstract description 22
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 claims abstract description 21
- 229910052765 Lutetium Inorganic materials 0.000 claims abstract description 20
- OHSVLFRHMCKCQY-UHFFFAOYSA-N lutetium atom Chemical compound [Lu] OHSVLFRHMCKCQY-UHFFFAOYSA-N 0.000 claims abstract description 20
- 229910001404 rare earth metal oxide Inorganic materials 0.000 claims abstract description 20
- 229910052688 Gadolinium Inorganic materials 0.000 claims abstract description 8
- 229910052746 lanthanum Inorganic materials 0.000 claims abstract description 8
- 229910052727 yttrium Inorganic materials 0.000 claims abstract description 8
- 239000007788 liquid Substances 0.000 claims description 26
- 230000008569 process Effects 0.000 claims description 22
- 238000005245 sintering Methods 0.000 claims description 19
- 239000000126 substance Substances 0.000 claims description 19
- 239000007789 gas Substances 0.000 claims description 17
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 16
- 239000012530 fluid Substances 0.000 claims description 16
- 238000002425 crystallisation Methods 0.000 claims description 15
- 238000010899 nucleation Methods 0.000 claims description 15
- 230000008025 crystallization Effects 0.000 claims description 14
- ADOANNTYRWJJIS-UHFFFAOYSA-N lutetium silicic acid Chemical compound [Lu].[Si](O)(O)(O)O ADOANNTYRWJJIS-UHFFFAOYSA-N 0.000 claims description 12
- 229910052757 nitrogen Inorganic materials 0.000 claims description 8
- 239000011261 inert gas Substances 0.000 claims description 4
- 238000000746 purification Methods 0.000 claims description 4
- 238000005516 engineering process Methods 0.000 description 20
- 238000002360 preparation method Methods 0.000 description 13
- -1 rare earth ion Chemical class 0.000 description 13
- 238000002156 mixing Methods 0.000 description 11
- 229910000422 cerium(IV) oxide Inorganic materials 0.000 description 10
- 229910052681 coesite Inorganic materials 0.000 description 10
- 229910052906 cristobalite Inorganic materials 0.000 description 10
- 239000000203 mixture Substances 0.000 description 10
- 229910052682 stishovite Inorganic materials 0.000 description 10
- 229910052905 tridymite Inorganic materials 0.000 description 10
- 238000005265 energy consumption Methods 0.000 description 9
- 229910003443 lutetium oxide Inorganic materials 0.000 description 8
- 229910000510 noble metal Inorganic materials 0.000 description 8
- 238000001816 cooling Methods 0.000 description 7
- 230000008901 benefit Effects 0.000 description 6
- CETPSERCERDGAM-UHFFFAOYSA-N ceric oxide Chemical compound O=[Ce]=O CETPSERCERDGAM-UHFFFAOYSA-N 0.000 description 6
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- 239000012071 phase Substances 0.000 description 6
- 230000007704 transition Effects 0.000 description 6
- 238000005520 cutting process Methods 0.000 description 5
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- 238000004364 calculation method Methods 0.000 description 4
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- 239000000843 powder Substances 0.000 description 4
- 239000007790 solid phase Substances 0.000 description 4
- 238000005303 weighing Methods 0.000 description 4
- 229910000420 cerium oxide Inorganic materials 0.000 description 3
- 230000008859 change Effects 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 230000006872 improvement Effects 0.000 description 3
- 238000002844 melting Methods 0.000 description 3
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- 230000004048 modification Effects 0.000 description 3
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- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 238000007796 conventional method Methods 0.000 description 2
- 238000001514 detection method Methods 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 238000004134 energy conservation Methods 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 description 2
- MPARYNQUYZOBJM-UHFFFAOYSA-N oxo(oxolutetiooxy)lutetium Chemical compound O=[Lu]O[Lu]=O MPARYNQUYZOBJM-UHFFFAOYSA-N 0.000 description 2
- 229910020187 CeF3 Inorganic materials 0.000 description 1
- 241000790917 Dioxys <bee> Species 0.000 description 1
- 229910002244 LaAlO3 Inorganic materials 0.000 description 1
- 229910003978 SiClx Inorganic materials 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 229910001632 barium fluoride Inorganic materials 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- LVEULQCPJDDSLD-UHFFFAOYSA-L cadmium fluoride Chemical compound F[Cd]F LVEULQCPJDDSLD-UHFFFAOYSA-L 0.000 description 1
- WUKWITHWXAAZEY-UHFFFAOYSA-L calcium difluoride Chemical compound [F-].[F-].[Ca+2] WUKWITHWXAAZEY-UHFFFAOYSA-L 0.000 description 1
- 229910001634 calcium fluoride Inorganic materials 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 230000001276 controlling effect Effects 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 230000001351 cycling effect Effects 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000002059 diagnostic imaging Methods 0.000 description 1
- 238000007713 directional crystallization Methods 0.000 description 1
- 230000005284 excitation Effects 0.000 description 1
- 150000002222 fluorine compounds Chemical class 0.000 description 1
- 230000008014 freezing Effects 0.000 description 1
- 238000007710 freezing Methods 0.000 description 1
- 150000004820 halides Chemical class 0.000 description 1
- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical compound I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 description 1
- 230000008676 import Effects 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 238000004020 luminiscence type Methods 0.000 description 1
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Classifications
-
- C—CHEMISTRY; METALLURGY
- C30—CRYSTAL GROWTH
- C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
- C30B15/00—Single-crystal growth by pulling from a melt, e.g. Czochralski method
-
- C—CHEMISTRY; METALLURGY
- C30—CRYSTAL GROWTH
- C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
- C30B15/00—Single-crystal growth by pulling from a melt, e.g. Czochralski method
- C30B15/20—Controlling or regulating
-
- C—CHEMISTRY; METALLURGY
- C30—CRYSTAL GROWTH
- C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
- C30B29/00—Single crystals or homogeneous polycrystalline material with defined structure characterised by the material or by their shape
- C30B29/10—Inorganic compounds or compositions
- C30B29/34—Silicates
Abstract
The present invention provides the growth techniques of low-cost rare earth scintillation crystal, comprise the following steps, first by RE2O3, after silica, the oxide of the oxide of cerium and lutetium mixed as raw material, obtain mixed raw material；The RE includes the one or more in Gd, La and Y；Then under vacuum or protective atmosphere, the mixed raw material that above-mentioned steps are obtained obtains polycrystal material block after oversintering；Finally under vacuum or protective atmosphere, after polycrystal material block is melted, under the guiding of the seed crystal with particular growth direction, after carrying out crystal growth using czochralski method, rare earth scintillating crystals are obtained.The present invention with reference to the bonding structure of the interface in rare earth scintillating crystals growth course, determines dominant growth direction, using the corresponding seed crystal with particular growth direction, so as to shorten the growth course time, reduces growth cost from crystal growth theories.
Description
Technical field
The present invention relates to scintillator crystal materials technical fields, and in particular to the growth of low-cost rare earth scintillation crystal.
Background technology
Scintillation crystal refers to, under the shock of the high energy particles such as X-ray and ray, can change the kinetic energy of high energy particle
The crystal to flash for luminous energy.And flicker and then refer to a kind of radioluminescence process, high-energy ray or high energy particle are converted
For ultraviolet or visible fluorescence pulse.Scintillation crystal main application fields have high-energy physics, nuclear physics, nuclear medicine (such as XCT, PET with
And g cameras), commercial Application (industry CT), geological prospecting, oil well logging etc..Scintillation crystal can send position under the excitation of ray
In the light wave of visible light wave range, different scintillator maximum flash transmission wavelength, photoyield, scintillation decay time, cascade unit,
The physical properties such as Radiation Hardness and density, fusing point, hardness, moisture absorption are all different.Commonly used scintillator crystal materials are all
It cultivates by artificial means, species is also very much, chemically has oxide, halide for ingredient (including iodide, fluorine
Compound) etc., the inorganic scintillator developed has NaI (Tl), CsI, CsI (Na), CsI (Tl), LiF (Eu), CaF2(Eu)、
CdF2、BaF2、CeF3、BGO(Bi3Ge4O12)、ZWO(ZnWO4)、CWO(CdWO)4、PWO(PbWO4)、GSO:Ce(Gd2SiO2O5:
Ce)、LAP:Ce(LaAlO3:Ce)、YAP:Ce(YAlO3:) and LSO Ce:Ce(Lu2Si2O5:Ce) etc., rare earth scintillating crystals are them
In important composition branch.Excellent luminance performance caused by rare earth ion uniqueness 4f electronic structures its become high activity shine in
The heart, the rare earth ion with the 4f electronic shell not being completely filled with share 1639 energy levels, it may occur however that the number of transition is up to
192177, therefore as a huge luminous treasure-house.Excellent luminance performance caused by rare earth ion uniqueness 4f electronic structures
It becomes the centre of luminescence of high activity, while rare earth element is due to can also be as the weight of host crystal with larger atomic number
It forms.What rare earth scintillating crystals were mainly studied at present be d-f transition, f-f transition correspond to it is ultraviolet to infrared characteristic absorption and
Emission process, such as Ce3+、Pr3+、Eu2+, they have 5d → 4f transition that complete spin-parity allows, substantially increase scintillator
Responding ability.Ce3+The scintillation crystal research of doping is the most extensive, it has the fast dipole allowed transitions of 5d → 4f, typical attenuation
Time is 10-50ns, meets scintillator to the demand for development that decays soon；And Y3+、La3+、Lu3+Wait rare earth ions lazy with optics
Property, the host material of luminescent material is suitable as, and the rare earth silicate series scintillation crystal of trivalent cerium ion doping is even more near
The high temperature scintillation crystal of new generation being concerned that a little years occur, for example, Ce:The light output of LSO crystal is about NaI (Tl) crystal
75%, be 7~10 times of BGO crystal, die-away time is only the 1/7 of BGO, and the density of the crystal and effective atomic number
Work as with BGO crystal phases.
Just because of the excellent flash detection performance of rare earth scintillating crystals, the height for being constantly subjected to researcher in the industry is closed
Note.But in practical applications, detector is critical component, and the spatial and temporal resolution of detection depends primarily upon scintillation crystal
Energy.In recent years, with the rapid development of electronic component, scintillation crystal cost quota shared in key detector but shows
Go out the trend rapidly increased.For example, scintillation crystal cost quota increases to 1/3 by past 1/6 in nuclear medical imaging device.
Therefore, the cost of rare earth scintillating crystals costliness has become the yoke in its application field, more hinders and further exists
Field of detecting is more widely applied, how to obtain the growth technique of low-cost rare earth scintillation crystal, it has also become application field
Forward position scholar's urgent problem to be solved.
The content of the invention
In view of this, the technical problem to be solved in the present invention is the growth technique for providing low-cost rare earth scintillation crystal,
The preparation method of the rare earth silicate scintillation crystal of especially inexpensive trivalent cerium ion doping, growth work provided by the invention
Skill, low energy consumption, and noble metal loss is few, and the growth course time is short, crystal high yield rate, has apparent low-cost advantage.
The present invention provides the growth techniques of low-cost rare earth scintillation crystal, comprise the following steps,
Anisotropic chemical bonding structure of the present invention at crystal growth interface, is determined using crystal growth theories
Dominant growth direction and the crystal growth parameters of calculation optimization；
A) by RE2O3, after silica, the oxide of the oxide of cerium and lutetium mixed as raw material, it is former to obtain mixing
Material；The RE includes the one or more in Gd, La and Y；
B) under vacuum or protective atmosphere, the mixed raw material that above-mentioned steps are obtained obtains polycrystal material after oversintering
Block；
Set the optimization crystal growth parameters obtained by theoretical calculation；
C) under vacuum or protective atmosphere, after polycrystal material block is melted, in drawing for the seed crystal with particular growth direction
It leads down, after carrying out crystal growth using czochralski method, obtains rare earth scintillating crystals.
Preferably, crystal orientation [100] direction of the seed crystal with particular growth direction, [010] direction or [001] side
To.
Preferably, the crystal growth theories are the chemical bonding theory of crystalline growth.
Preferably, the seed crystal is silicic acid lutetium monocrystalline.
Preferably, the temperature of the guiding is 1850~2050 DEG C.
Preferably, the step c) is specially：
Under vacuum or protective atmosphere, heat up polycrystal material block, when there is feature liquid fluid line, using described with specific
The seed crystal of the direction of growth carries out seeding operation, after then carrying out crystal growth using czochralski method, obtains rare earth scintillating crystals.
Preferably, during the crystal growth, growth rate is 2.5~8.0mm/h, Crystal Rotation rate for 6~
30rpm。
Preferably, the RE2O3, cerium oxide and lutetium oxide quality sum and silica quality ratio
It is worth for (0.75~1.25)：1；The quality of the oxide of the cerium and the RE2O3With the ratio of the quality sum of the oxide of lutetium
For (0.005~0.04)：1；The RE2O3Mass ratio with the oxide of lutetium is (0.005~1)：1.
Preferably, further included before the step a) and the raw material is subjected to purification processes by multistage crystallization technique；
In the raw material, the RE2O3, silica, the purity of oxide of the oxide of cerium and lutetium is all higher than being equal to
99.995%.
Preferably, further included after the step a), by mixed raw material after cake of press, obtain raw material cake；The cake of press
Pressure be 20~70MPa；The temperature of the sintering is 900~1300 DEG C.
Preferably, the protective atmosphere is the one or more in nitrogen, inert gas and reducibility gas.
The present invention provides the growth techniques of low-cost rare earth scintillation crystal, comprise the following steps, first by RE2O3, dioxy
After the oxide of SiClx, the oxide of cerium and lutetium is mixed as raw material, mixed raw material is obtained；The RE includes Gd, La and Y
In one or more；Then under vacuum or protective atmosphere, the mixed raw material that above-mentioned steps are obtained obtains after oversintering
To polycrystal material block；Finally under vacuum or protective atmosphere, after polycrystal material block is melted, in the seed crystal with particular growth direction
Guiding under, using czochralski method carry out crystal growth after, obtain rare earth scintillating crystals.Compared with prior art, it is of the invention from crystalline substance
Body growth theory sets out, and with reference to the bonding structure of the interface in rare earth scintillating crystals growth course, determines dominant growth direction,
Using the corresponding seed crystal with particular growth direction, so as to shorten the growth course time, growth cost is reduced.The present invention
The growth technique of offer, low energy consumption, and noble metal loss is few, and the growth course time is short, crystal high yield rate, have it is apparent it is low into
This advantage.The experimental results showed that the experimental results showed that, growth technique provided by the invention has relatively low phase transformation temperature points, phase
It is more most than original technology to reduce 8.7%, and preparation time short when small (96 within) reduce compared to original technology (30%~
50%), crystal yield rate can reach more than 80%, and the rare earth scintillating crystals prepared compared to original technology add about 60%.
Description of the drawings
Fig. 1 is the XRD spectra of rare earth scintillating crystals prepared by the embodiment of the present invention 1.
Specific embodiment
For a further understanding of the present invention, the preferred embodiment of the invention is described with reference to embodiment, still
It should be appreciated that these descriptions are intended merely to the feature and advantage further illustrated the present invention rather than to invention claim
Limitation.
All raw materials of the present invention, are not particularly limited its source, buying on the market or according to people in the art
Known to member prepared by conventional method.
All raw materials of the present invention, are not particularly limited its purity, pure present invention preferably employs analyzing.
The present invention provides the growth techniques of low-cost rare earth scintillation crystal, comprise the following steps,
The present invention utilizes the chemical bonding theory of crystalline growth, the interface in rare earth scintillating crystals growth course
Bonding structure, respectively calculate rare earth scintillating crystals vertically (dip direction) and radially (perpendicular to dip direction) grow it is opposite
Growth rate determines dominant growth direction and calculating and optimizes the growth parameter(s) grown in the direction；
A) by RE2O3, after silica, the oxide of the oxide of cerium and lutetium mixed as raw material, it is former to obtain mixing
Material；The RE includes the one or more in Gd, La and Y；
B) under vacuum or protective atmosphere, the mixed raw material that above-mentioned steps are obtained obtains polycrystal material after oversintering
Block；
C) under vacuum or protective atmosphere, after polycrystal material block is melted, in drawing for the seed crystal with particular growth direction
It leads down, after carrying out crystal growth using czochralski method, obtains rare earth scintillating crystals.
The present invention is first by RE2O3, after silica, the oxide of the oxide of cerium and lutetium mixed as raw material, obtain
To mixed raw material；The RE includes the one or more in Gd, La and Y；
Raw material of the present invention preferably includes RE2O3, silica, the oxide of the oxide of cerium and lutetium；Stating RE includes
One or more in Gd, La and Y, more preferably Gd, La or Y.The oxide of the cerium is not particularly limited in the present invention, with
The oxide of cerium well known to those skilled in the art, the present invention are preferably CeO2；The present invention does not have the oxide of the lutetium
There is special limitation, with the oxide of lutetium well known to those skilled in the art, the present invention is preferably Lu2O3。
The present invention especially limits the raw material without other, with the property of above-mentioned raw materials well known to those skilled in the art
, the present invention enhances product performance and yield rate further to reduce production cost, preferably before the mixing, first will
Raw material is respectively to get to high pure raw material after multistage crystallization technique carries out purification processes.The present invention is to the multistage crystallization work
The definition of skill is not particularly limited, with the definition of multistage crystallization technique well known to those skilled in the art, i.e., multistage tandem
Crystallization processes or recrystallization method, multistage crystallization technique of the present invention preferably refer to, after carrying out feedstock purification using crystallization processes,
The raw material of acquisition is crystallized again, high pure raw material is obtained after cycling repeatedly crystallization.The present invention is to the specific step of the crystallization processes
Suddenly be not particularly limited, with crystallization processes step well known to those skilled in the art, the present invention be preferably liquid phase crystallization method,
Selective freezing method, directional crystallization method, more preferably aqueous solution crystalgrowing method.The present invention is not special to the purity of the high pure raw material
Limitation, those skilled in the art can make choice and adjust according to practical condition, raw material composition and properties of product requirement
Whole, the present invention is preferably greater than to be equal to 99.995%, more preferably higher than equal to 99.997%, is most preferably more than or equal to
99.999%.Other properties of the high pure raw material are not particularly limited in the present invention, with system well known to those skilled in the art
The property of the raw material of standby rare earth scintillating crystals, the granularity of high pure raw material of the present invention is preferably 0.05~30 μm, more excellent
Elect 0.1~25 μm as, more preferably 1~20 μm, be most preferably 5~15 μm.
The present invention obtains height using multistage crystallization technique, i.e., the rare earths material of multistage tandem crystallization processes purifying low cost
The raw material of purity, had not only improved the utilization rate of raw material, but also improved the quality and yield rate of product, so as to saved raw material into
This.
The condition of the mixing is not particularly limited in the present invention, with the mixed of such reaction well known to those skilled in the art
Conjunction condition, those skilled in the art can be adjusted according to practical condition, raw material condition, and the present invention is preferably equal
Even mixing, the time of the mixing is preferably 24~120h, more preferably 30~100h, more preferably 40~90h, is most preferably
60~80h.The mode of the mixing is not particularly limited in the present invention, with hybrid mode well known to those skilled in the art, sheet
Invention is preferably mixed using blender.
The present invention is to the RE2O3, silica, the oxide of cerium and lutetium oxide between ratio do not limit especially
System, those skilled in the art can make choice and adjust according to practical condition, raw material composition and properties of product requirement,
The present invention combines for further optimizing raw material, reduces the controllable degree of subsequent technique, RE of the present invention2O3, cerium oxide and
The ratio of the quality sum of the oxide of lutetium and the quality of silica, i.e. (CeRELu)2O3:SiO2Preferably (0.75~
1.25)：1, more preferably (0.80~1.2)：1, more preferably (0.85~1.15)：1, be most preferably (0.9~1.1)：1；Institute
State the quality of the oxide of cerium and the RE2O3With the ratio of the quality sum of the oxide of lutetium, i.e. CeO2:(RE2O3+Lu2O3)
Preferably (0.005~0.04)：1, more preferably (0.01~0.035)：1, more preferably (0.015~0.03)：1, most preferably
For (0.02~0.025)：1；The RE2O3Mass ratio with the oxide of lutetium is preferably (0.005~1)：1, more preferably
(0.01~0.8)：1, more preferably (0.05~0.5)：1, be most preferably (0.1~0.3)：1.
Other properties of the mixed raw material are not particularly limited in the present invention, with preparation well known to those skilled in the art
The property of the mixed raw material of rare earth scintillating crystals, the granularity of mixed raw material of the present invention is preferably 0.05~30 μm, more
Preferably 0.1~25 μm, more preferably 1~20 μm are most preferably 5~15 μm.
The present invention further refines rare earth scintillating crystals raw material by optimizing the composition of congruent melting area inner oxide raw material
So as to reduce liquid/solid phase transformation temperature points in subsequent crystallographic growth course, rare earth sudden strain of a muscle is reduced to reach for ratio during preparation
Bright crystal growth temperature, so as to reduce the purpose of energy consumption.The present invention is formed by regulating and controlling congruent melting area inner oxide raw material, will
Liquid/solid phase transformation temperature points are reduced to 1850 DEG C or so from existing 2050 DEG C, can be effective compared to reducing 8.7% before improvement
The intermediate frequency power supply power of subsequent crystallographic growth course is reduced, the energy consumption in growth course is reduced, has saved production cost, effectively
Solve in existing rare earth silicate scintillation crystal preparation process fusing point height (2050 DEG C), in crystal growing process energy consumption it is big,
Serious inherent shortcoming is lost in noble metal；And the growth technique of follow-up rare earth scintillating crystals is combined, it is common to realize rare earth flicker
The low cost growth of crystal.In addition, crystal raw material prepares the proportioning for being capable of Effective Regulation rare earth scintillating crystals composition, be conducive to
The controllable adjustment of scintillation properties.
Then under vacuum or protective atmosphere, the mixed raw material that above-mentioned steps are obtained obtains the present invention after oversintering
To polycrystal material block.
The pressure of the vacuum is not particularly limited in the present invention, with the true of sintering process well known to those skilled in the art
Pneumatics power, the pressure of vacuum of the present invention, which is preferably less than, is equal to 10Pa, more preferably less than equal to 1Pa, more preferably
It is most preferably 0.01~0.3Pa to be less than or equal to 0.3Pa；The protective atmosphere is not particularly limited in the present invention, with ability
The protective atmosphere of sintering rare-earth crystal is used for known to field technique personnel, protective atmosphere of the present invention to be preferably nitrogen
One or more in gas, inert gas and reducibility gas, more preferably nitrogen and reducibility gas, be most preferably nitrogen and
Hydrogen.
The actual conditions of the sintering is not particularly limited in the present invention, with sintering condition well known to those skilled in the art
, the temperature of sintering of the present invention is preferably 900~1300 DEG C, more preferably 950~1250 DEG C, more preferably 1000~
1200 DEG C, be most preferably 1050~1150 DEG C.The time of sintering of the present invention is preferably 12~20h, more preferably 13~
19h, more preferably 14~18h are most preferably 15~17h.The equipment of the sintering is not particularly limited in the present invention, with ability
The mixed raw material is preferably put into high-purity crucible in sintering furnace by agglomerating plant known to field technique personnel, the present invention
Sintering.
The present invention is to reach better sintering effect, after mixed raw material further preferably is first passed through cake of press, obtains raw material cake, then
It is sintered.The specific steps and technological parameter of the cake of press are not particularly limited in the present invention, ripe with those skilled in the art
The specific steps and technological parameter of green compact before the sintering known, those skilled in the art can be according to practical condition, originals
Material composition and properties of product requirement make choice and adjust, and the pressure of cake of press of the present invention is preferably 20~70MPa, more excellent
It elects 30~60MPa as, is most preferably 40~50MPa.
The present invention is finally under vacuum or protective atmosphere, and the polycrystal material block that above-mentioned steps are obtained is with particular growth
Under the guiding of the seed crystal in direction, after carrying out crystal growth using czochralski method, rare earth scintillating crystals are obtained.
The pressure of the vacuum is not particularly limited in the present invention, with the true of sintering process well known to those skilled in the art
Pneumatics power, the pressure of vacuum of the present invention, which is preferably less than, is equal to 10Pa, more preferably less than equal to 1Pa, more preferably
It is most preferably 0.01~0.3Pa to be less than or equal to 0.3Pa；The protective atmosphere is not particularly limited in the present invention, with ability
The protective atmosphere of sintering rare-earth crystal is used for known to field technique personnel, protective atmosphere of the present invention to be preferably nitrogen
One or more in gas, inert gas and reducibility gas, more preferably nitrogen and reducibility gas, be most preferably nitrogen and
Hydrogen.
The seed crystal is not particularly limited in the present invention, and rare earth flicker crystalline substance is used to prepare with well known to those skilled in the art
The seed crystal of body, the present invention are preferably silicic acid lutetium monocrystalline.Rate and definite dominant growth of the present invention for raising crystal growth
Direction, it is preferred to use there is the seed crystal in particular growth direction；The crystal orientation of the seed crystal with particular growth direction is more preferably
[100] direction, [010] direction or [001] direction.
The temperature (seeding temperature) of guiding of the present invention is preferably 1850~2050 DEG C, and more preferably 1880~2000
DEG C, more preferably 1900~1970 DEG C, be most preferably 1920~1950 DEG C.
The present invention is further optimization crystal growing process, improves the rate of crystal growth and the controllability of growth, this hair
Bright above-mentioned steps are particularly preferred as preparing the seed crystal with particular growth direction；Heat up (heating) polycrystal material block, feature is occurring
During liquid fluid line, seeding operation is carried out using the seed crystal, after then carrying out crystal growth using czochralski method, it is brilliant to obtain rare earth flicker
Body；More preferably first prepare the seed crystal with particular growth direction；Heat up polycrystal material block again, when there is feature liquid fluid line, makes
Seeding operation is carried out with the seed crystal, after then carrying out crystal growth using czochralski method, obtains rare earth scintillating crystals.
The source of the seed crystal with particular growth direction is not particularly limited in the present invention, and those skilled in the art can
To prepare according to conventional methods or commercially available purchase, the present invention is preferably by being obtained after proembryo crystalline substance directional cutting.The present invention is to described
The definition of proembryo crystalline substance is not particularly limited, and with the definition of proembryo well known to those skilled in the art crystalline substance, the present invention is preferably
Refer to the crystal of the crystal of seed crystal, more preferably silicic acid lutetium monocrystalline；The directional cutting is not particularly limited in the present invention, with ability
The definition of directional cutting known to field technique personnel, directional cutting of the present invention preferably refer to crystal orientation with reference to the direction of growth into
Row cutting.
The temperature-rise period of the heating polycrystal material block is not particularly limited in the present invention, with well known to those skilled in the art
Temperature-rise period.Seeding operation of the present invention is preferably carried out when there is feature liquid fluid line (liquid fluid line).Art technology
Personnel are it is understood that liquid fluid line refers to curve tangent all with rate vector on every bit in fluid liquid field.Institute of the present invention
State occur feature liquid fluid line in macroscopical presentation be preferably, polycrystal material block liquid phase is become from solid phase after when ripple occurs in liquid phase surface
When, as there is feature liquid fluid line.
The present invention is guided after there is feature liquid fluid line using seed crystal, then carries out crystal growth using czochralski method,
Obtain rare earth scintillating crystals.The czochralski method is not particularly limited in the present invention, with it is well known to those skilled in the art prepare it is dilute
The czochralski method of native scintillation crystal；The technological parameter of the czochralski method is not particularly limited in the present invention, people in the art
Member can make choice and adjust according to practical condition, raw material composition and properties of product requirement.
The rate of crystal growth of the present invention is preferably 2.5~8.0mm/h, more preferably 4~7.5mm/h, more preferably
It is most preferably 5.5~6.5mm/h for 5.1~7.0mm/h；The Crystal Rotation rate is preferably 6~30rpm, and more preferably 8
~25rpm, more preferably 10~22rpm are most preferably 10~18rpm.The present invention does not have the size of the rare earth scintillating crystals
There is special limitation, those skilled in the art can be selected according to practical condition, raw material composition and properties of product requirement
It selects and adjusts, the equal-diameter part of rare earth scintillating crystals of the present invention is preferably cylindrical type, the diameter of the rare earth scintillating crystals
Preferably 1.5~4 inches, more preferably 2~3.5 inches are most preferably 2~3.0 inches；The height of the rare earth scintillating crystals
Preferably 60~150mm, more preferably 70~130mm are most preferably 90~110mm.
It will be appreciated by those skilled in the art that the speed of rare earth scintillating crystals growth rate and the size of rare earth scintillating crystals
There are association, under equal conditions, the size of rare earth scintillating crystals is bigger, and the growth rate of rare earth scintillating crystals then needs to slow down,
Rare earth scintillating crystals size is smaller, and the growth rate of rare earth scintillating crystals can be faster.Rare earth scintillating crystals of the present invention
Volume growth rate is preferably 6.22~9.64cm3/ h has more objective practical significance.
The present invention, into temperature-fall period, after being down to room temperature (20~30 DEG C), obtains dilute further preferably after crystal growth
Native scintillation crystal.The processing step and parameter of the temperature-fall period is not particularly limited in the present invention, with those skilled in the art
Well known cooling step and parameter, those skilled in the art can be according to practical condition, raw material composition and products
Performance requirement makes choice and adjusts, and the present invention is preferably the cooling of multistage staged.
Above-mentioned steps of the present invention are more specifically preferably that round pie polycrystal material is tired out to closed assembly successively first enters crystal growth burner hearth
In Ir crucibles in, in the front loaded seed crystal with particular growth direction of seed rod, seed crystal is placed in the surface of polycrystal material block；
Then inertia or partly reducing atmosphere are re-filled with after burner hearth is vacuumized as protection gas, heat up melt；Treat the polycrystalline of liquid
When feature liquid fluid line (ripple) occurs in material surface, seed crystal is contacted into liquid level, rear slowly lifting seed crystal guides；Then according to spy
Fixed growth rate and the speed of rotation realize that the fast-growth of rare earth scintillating crystals, growth, into temperature-fall period, are set after terminating
Multistage cooling process, is cooled to room temperature temperature, and crystal is taken out in blow-on.
The present invention is from crystal growth theories, with reference to the bonding junction of the interface in rare earth scintillating crystals growth course
Structure determines dominant growth direction and calculating and optimizes the growth parameter(s) grown in the direction, such as pulling growth rate and rotation
Rate, moreover it is possible to according to the most fast growth rate allowed in the rare earth scintillating crystals control growth course of different isometrical sizes, build
Matching temperature environment realizes the fast-growth of rare earth scintillating crystals.
Rare earth scintillating crystals have been prepared by above-mentioned steps in the present invention.The present invention is directed to crystal growth in the prior art
Crystal quality deficiency in technology, production cost is excessively high, and crucial high pure raw material needs import, it is expensive the problems such as, from production
The various aspects of process carry out comprehensive analysis, main reason is that rare earth silicate scintillation crystal fusing point height (2050 DEG C), higher
Fusing point medium/high frequency power can be caused to expend higher electric energy, and rare earth silicate scintillation crystal fusing point in heating process
Close to the fusing point (2450 DEG C) of calandria Ir crucibles, Ir volatilizations are serious, and longer growth cycle causes noble metal loss serious, and
And during conventional growth, to prevent rare earth silicate scintillation crystal from cracking, its growth rate reduction causes growth cycle long,
Cause growth course human cost input high.In conclusion in crystal growing process, high energy consumption, noble metal loss are serious, raw
Growth process human cost input is high, crystal yield rate is low so that rare earth silicate scintillation crystal growth cost remains high.
The present invention starts with from raw material preparation, and the relatively low rare earths material of price is carried out secondary carry using multistage crystallization technique
It is pure, the high-purity rare-earth raw material of low cost is obtained, improves the utilization rate of raw material, the quality of product and yield rate；The present invention passes through
Optimize the composition of congruent melting area inner oxide raw material, that is, rare earth scintillating crystals raw material configuration proportion is refined, so as to reduce crystal
Liquid/solid phase transformation temperature points in growth course reduce rare earth scintillating crystals growth temperature to reach, so as to reduce the purpose of energy consumption,
The intermediate frequency power supply power of subsequent crystallographic growth course can be effectively reduced, the energy consumption in growth course is reduced, has saved and be produced into
This；Invention is further from crystal growth theories, with reference to the bonding structure of the interface in rare earth scintillating crystals growth course,
It determines dominant growth direction, using the seed crystal of corresponding crystal orientation and calculating and optimizes the growth parameter(s) grown in the direction, such as carry
Draw growth rate and the speed of rotation, moreover it is possible to allow most according in the rare earth scintillating crystals control growth course of different isometrical sizes
Fast growth rate, builds matching temperature environment, finally realizes the fast-growth of rare earth scintillating crystals, reduces growth
Cost.
The experimental results showed that growth technique provided by the invention has relatively low phase transformation temperature points, compared to original technology most
It is reduce 8.7%, and preparation time short when small (96 within) reduces (30%~50%) compared to original technology more, crystal into
Product rate can reach more than 80%, and the rare earth scintillating crystals prepared compared to original technology add about 60%.
In order to further illustrate the present invention, with reference to embodiment to low-cost rare earth scintillation crystal provided by the invention
Growth technique is described in detail, and protection scope of the present invention is not limited by the following examples.
Embodiment 1
According to above-mentioned preparation process, by Lu2O of the purity higher than 99.995%3、SiO2And CeO2Powder, according to Lu2O3:
SiO2:CeO2=1.19:1:0.01 proportioning weighing, carries out abundant batch mixing, raw material cake is pressed under 45MPa, raw material cake is put into
Sintering forms polycrystal material block at 1200 DEG C under inert atmosphere protection after high-purity crucible.Utilize the chemical bonding theory of crystalline growth
It calculates and determines dominant growth direction [100], take the silicic acid lutetium monocrystalline that crystal orientation is [100] direction as seed crystal.Utilize crystal growth
Pulling growth rate 3.0~5.5mm/h, the speed of rotation 10~25rpm of the theoretical calculation cerium dopping silicic acid lutetium along [100] direction.
5500g round pies polycrystal material is tired out to closed assembly successively to enter in the Ir crucibles in crystal growth burner hearth, is had seed rod is front loaded
[100] seed crystal of the direction of growth.Burner hearth is filled with partly reducing atmosphere Ar+H after vacuumizing2Gas is as protection gas, and heat up melt
(polycrystal material block).
When feature liquid fluid line (ripple) occurs in the polycrystal material surface of liquid, seed crystal is contacted into liquid level, rear slowly lifting seed
Crystalline substance guides, and seeding temperature is 2010 DEG C, after seeding, is realized according to the growth rate and the speed of rotation that calculate acquisition dilute
The fast-growth of native scintillation crystal, the pulling growth rate of crystal are 2.8~5.0mm/h, maximum Crystal Rotation rate for 12~
25rpm.Growth enters temperature-fall period after terminating, and sets multistage cooling process, is cooled to room temperature temperature, and crystal is taken out in blow-on.
Above-mentioned steps of the present invention are counted, the results showed that, crystal growth has relatively low phase transition temperature in the present invention
Point (seeding temperature), 6.3% is reduced compared to original technology, can effectively reduce intermediate frequency power supply power, is reduced in growth course
Energy consumption, saved production cost burner hearth, and preparation time for 94 it is small when, reduce 35% compared to original technology, crystal into
Product rate is 80%, adds 60% compared to original technology, the growth course electricity consumption of crystal is 1615kWh, than conventional growth mistake
Cheng Jieneng 25.63%, noble metal Ir volatilization reduce 5.2g, when growth course time cripetura short 23 is small.Growth provided by the invention
Rare earth scintillating crystals prepared by technique, holistic cost have dropped about 12% compared to rare earth scintillating crystals prepared by original technology, tool
There is apparent low-cost advantage.
The rare earth scintillating crystals prepared to above-mentioned steps of the present invention are detected, and referring to Fig. 1, Fig. 1 is the embodiment of the present invention 1
The XRD spectra of the rare earth scintillating crystals of preparation.As shown in Figure 1, the rare earth scintillating crystals quality that prepared by above-mentioned steps of the present invention is good
It is good.
Embodiment 2
According to above-mentioned preparation process, by Lu of the purity higher than 99.995%2O3、SiO2、CeO2Powder, according to Lu2O3：
SiO2：CeO2=1.19：1：0.01 proportioning weighing, carries out abundant batch mixing, raw material cake is pressed under 50MPa, raw material cake is put into
Sintering forms polycrystal material block at 900 DEG C under inert atmosphere protection after high-purity crucible.Utilize the chemical bonding theory of crystalline growth
It calculates and determines dominant growth direction [100], take the silicic acid lutetium monocrystalline that crystal orientation is [100] direction as seed crystal.Utilize crystal growth
Pulling growth rate 4.0~6.5mm/h, the speed of rotation 10~25rpm of the theoretical calculation cerium dopping silicic acid lutetium along [100] direction.
2800g round pies polycrystal material is tired out to closed assembly successively to enter in the Ir crucibles in crystal growth burner hearth, is had seed rod is front loaded
[100] seed crystal of the direction of growth.Burner hearth is filled with inert atmosphere Ar gas as protection gas after vacuumizing, heat up melt.
When feature liquid fluid line (ripple) occurs in the polycrystal material surface of liquid, seed crystal is contacted into liquid level, rear slowly lifting seed
Crystalline substance guides, and seeding temperature is 2010 DEG C, after seeding, is realized according to the growth rate and the speed of rotation that calculate acquisition dilute
The fast-growth of native scintillation crystal, the pulling growth rate of crystal are 4.0~6.5mm/h, Crystal Rotation rate for 10~
25rpm.Growth enters temperature-fall period after terminating, and sets multistage cooling process, is cooled to room temperature temperature, and crystal is taken out in blow-on.
Above-mentioned steps of the present invention are counted, the results showed that, when growth course time cripetura short 13 is small, crystal yield rate
For 80%, 60% is added compared to original technology, the growth course electricity consumption 515kWh of crystal is more energy saving than conventional growth
31.85%, noble metal Ir volatilization reduce 1.5g, rare earth scintillating crystals prepared by growth technique provided by the invention, holistic cost
The rare earth scintillating crystals prepared compared to original technology have dropped about 15%, have apparent low-cost advantage.
Embodiment 3
According to above-mentioned preparation process, by Lu of the purity higher than 99.995%2O3、Y2O3、SiO2、CeO2Powder, according to Lu2O3:
Y2O3:SiO2:CeO2=0.83:0.36:1:0.01 proportioning weighing, carries out abundant batch mixing, raw material cake is pressed under 50MPa, will
Raw material cake is put into after high-purity crucible under inert atmosphere protection sintering at 1050 DEG C and forms polycrystal material block.Utilize the change of crystalline growth
It learns bond theory and calculates definite dominant growth direction [001], take the silicic acid lutetium monocrystalline that crystal orientation is [001] direction as seed crystal.Profit
Pulling growth rate 5.0-7.5mm/h, speed of rotation 8- of the cerium dopping silicic acid lutetium along [001] direction are calculated with crystal growth theories
20rpm.2800g round pies polycrystal material is tired out to closed assembly successively to enter in the Ir crucibles in crystal growth burner hearth, is filled in seed rod front end
Enter there is the seed crystal of [001] direction of growth.Burner hearth is filled with inert atmosphere Ar gas as protection gas after vacuumizing, heat up melt.
When feature liquid fluid line (ripple) occurs in the polycrystal material surface of liquid, seed crystal is contacted into liquid level, rear slowly lifting seed
Crystalline substance guides, and seeding temperature is 1940 DEG C, after seeding, is realized according to the growth rate and the speed of rotation that calculate acquisition dilute
The fast-growth of native scintillation crystal, the pulling growth rate of crystal is 5.0~7.5mm/h, 8~20rpm of the speed of rotation.Grown junction
Into temperature-fall period after beam, multistage cooling process is set, is cooled to room temperature temperature, crystal is taken out in blow-on.
Above-mentioned steps of the present invention are counted, the results showed that, when crystal growth time is 28 small in the present invention, compared to original
There is technology to reduce 39.4%, the growth course electricity consumption of crystal is 505kWh, expensive than conventional growth process energy conservation 27.32%
Metal Ir volatilizations reduce 5.2g, when growth course time cripetura short 12 is small.Rare earth prepared by growth technique provided by the invention dodges
Bright crystal, holistic cost have dropped about 14% compared to rare earth scintillating crystals prepared by original technology, excellent with apparent low cost
Gesture.
Embodiment 4
According to above-mentioned preparation process, by Lu of the purity higher than 99.995%2O3、Y2O3、SiO2、CeO2Powder, according to Lu2O3:
Y2O3:SiO2:CeO2=0.83:0.36:1:0.01 proportioning weighing, carries out abundant batch mixing, raw material cake is pressed under 50MPa, will
Raw material cake is put into after high-purity crucible under inert atmosphere protection sintering at 1050 DEG C and forms polycrystal material block.Utilize the change of crystalline growth
It learns bond theory and calculates definite dominant growth direction [010], take the silicic acid lutetium monocrystalline that crystal orientation is [010] direction as seed crystal.Profit
Pulling growth rate 3.8~6.2mm/h of the cerium dopping silicic acid lutetium along [010] direction, the speed of rotation are calculated with crystal growth theories
10~24rpm.5500g round pies polycrystal material is tired out to closed assembly successively to enter in the Ir crucibles in crystal growth burner hearth, before seed rod
End is packed into the seed crystal with [010] direction of growth.Burner hearth is filled with partly reducing atmosphere Ar+H after vacuumizing2Gas is as protection
Gas, heat up melt.
When feature liquid fluid line (ripple) occurs in the polycrystal material surface of liquid, seed crystal is contacted into liquid level, rear slowly lifting seed
Crystalline substance guides, and seeding temperature is 1930 DEG C, after seeding, is realized according to the growth rate and the speed of rotation that calculate acquisition dilute
The fast-growth of native scintillation crystal, the pulling growth rate of crystal is 3.8~6.2mm/h, 10~24rpm of the speed of rotation.Growth
After into temperature-fall period, set multistage cooling process, be cooled to room temperature temperature, crystal is taken out in blow-on.
Above-mentioned steps of the present invention are counted, the results showed that, when crystal growth time is 72 small in the present invention, compared to original
There is technology to reduce 35%, crystal yield rate is 80%, adds 60% compared to original technology, the growth course electricity consumption of crystal is
1615kWh, than conventional growth process energy conservation 25.63%, noble metal Ir volatilizations reduce 5.2g, and the cripetura of growth course time is short by 23
Hour.Rare earth scintillating crystals prepared by growth technique provided by the invention, holistic cost are dodged compared to rare earth prepared by original technology
Bright crystal has dropped about 11%, has apparent low-cost advantage.
The explanation of above example is only intended to help to understand method and its core concept of the invention.It should be pointed out that pair
For those skilled in the art, without departing from the principle of the present invention, the present invention can also be carried out
Several improvement and modification, these improvement and modification are also fallen into the protection domain of the claims in the present invention.
The foregoing description of the disclosed embodiments enables professional and technical personnel in the field to realize or use the present invention.
A variety of modifications of these embodiments will be apparent for those skilled in the art, it is as defined herein
General Principle can be realized in other embodiments without departing from the spirit or scope of the present invention.Therefore, it is of the invention
The embodiments shown herein is not intended to be limited to, and is to fit to and the principles and novel features disclosed herein phase one
The most wide scope caused.
Claims (8)
1. the growth technique of low-cost rare earth scintillation crystal, which is characterized in that comprise the following steps,
a）By RE2O3, after silica, the oxide of the oxide of cerium and lutetium mixed as raw material, obtain mixed raw material；
The raw material includes RE2O3, silica, the oxide of the oxide of cerium and lutetium；The RE is included in Gd, La and Y
One or more；
The RE2O3, the oxide of cerium and the ratio with the amount of the substance of the silica of the sum of the amount of substance of oxide of lutetium
It is worth for more than or equal to 0.75 and less than 1 or for more than 1 and less than or equal to 1.25；
The amount of the substance of the oxide of the cerium and the RE2O3Ratio with the sum of the amount of substance of oxide of lutetium is
（0.005~0.04）：1；
The RE2O3Ratio with the amount of the substance of the oxide of lutetium is（0.005~1）：1；
b）Under vacuum or protective atmosphere, the mixed raw material that above-mentioned steps are obtained obtains polycrystal material block after oversintering；
c）Under vacuum or protective atmosphere, after polycrystal material block is melted, under the guiding of the seed crystal with particular growth direction,
After carrying out crystal growth using czochralski method, rare earth scintillating crystals are obtained；
The temperature of the guiding is more than or equal to 1850 and less than 2050 DEG C.
2. growth technique according to claim 1, which is characterized in that the crystal orientation of the seed crystal with particular growth direction
[100] direction, [010] direction or [001] direction.
3. growth technique according to claim 1, which is characterized in that the seed crystal is silicic acid lutetium monocrystalline.
4. growth technique according to claim 1, which is characterized in that the step c）Specially：
Under vacuum or protective atmosphere, heat up polycrystal material block, when there is feature liquid fluid line, has particular growth using described
The seed crystal in direction carries out seeding operation, after then carrying out crystal growth using czochralski method, obtains rare earth scintillating crystals.
5. growth technique according to claim 1, which is characterized in that during the crystal growth, growth rate is
2.5 ~ 8.0 mm/h, Crystal Rotation rate are 6 ~ 30 rpm.
6. growth technique according to claim 1, which is characterized in that the step a）It further includes before and passes through the raw material
It crosses multistage crystallization processes and carries out purification processes；
In the raw material, the RE2O3, silica, the purity of oxide of the oxide of cerium and lutetium is all higher than being equal to
99.995% 。
7. growth technique according to claim 1, which is characterized in that the step a）It further includes afterwards, by mixed raw material
After cake of press, raw material cake is obtained；The pressure of the cake of press is 20 ~ 70MPa；The temperature of the sintering is 900 ~ 1300 DEG C.
8. growth technique according to claim 1, which is characterized in that the protective atmosphere for nitrogen, inert gas and
One or more in reducibility gas.
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| CN106757354A (en) * | 2017-01-24 | 2017-05-31 | 中国科学院长春应用化学研究所 | The growth of low-cost rare earth scintillation crystal |
| CN106835270A (en) * | 2017-01-24 | 2017-06-13 | 中国科学院长春应用化学研究所 | The growth of low-cost rare earth scintillation crystal |
| CN107740188A (en) * | 2017-09-04 | 2018-02-27 | 中国科学院长春应用化学研究所 | The computational methods and computing system of pulling growth speed in the growth technique of low-cost rare earth crystal |
| CN110344117A (en) * | 2019-07-04 | 2019-10-18 | 南京同溧晶体材料研究院有限公司 | Rare earth ion doped oxidation lanthanum lutetium fast flashing crystal of one kind and its preparation method and application |
| CN111910254A (en) * | 2020-08-04 | 2020-11-10 | 南昌大学 | Cerium-doped and erbium-doped ytterbium silicate scintillation crystal and preparation method thereof |
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| CN1250526A (en) * | 1998-01-12 | 2000-04-12 | Tasr有限公司 | Scintillating substance and scintillating wave-guide element |
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| CN103757708A (en) * | 2014-01-17 | 2014-04-30 | 中国科学院福建物质结构研究所 | High temperature inorganic scintillation crystal growth crucible |
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| CN1283852C (en) * | 2003-11-14 | 2006-11-08 | 中国科学院上海光学精密机械研究所 | Method for growing gadolinium orthosilicate scintillation crystal |
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| CN1250526A (en) * | 1998-01-12 | 2000-04-12 | Tasr有限公司 | Scintillating substance and scintillating wave-guide element |
| CN1552957A (en) * | 2003-12-19 | 2004-12-08 | 中国科学院上海光学精密机械研究所 | Preparation of divalent cerium ion dosed rare earth silicate scintillating crystal |
| CN103757708A (en) * | 2014-01-17 | 2014-04-30 | 中国科学院福建物质结构研究所 | High temperature inorganic scintillation crystal growth crucible |
| CN104073877A (en) * | 2014-06-27 | 2014-10-01 | 成都东骏激光股份有限公司 | Method for growing cerium-doped lutetium yttrium scintillation orthosilicate crystal by virtue of Bridgman-Stockbarger method |
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