CN108218417A - A kind of LuAG of lower valency ion doping:Ce, Me scintillating ceramic and preparation method thereof - Google Patents
A kind of LuAG of lower valency ion doping:Ce, Me scintillating ceramic and preparation method thereof Download PDFInfo
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Abstract
The present invention relates to a kind of LuAG of lower valency ion doping:Ce, Me scintillating ceramic and preparation method thereof, the composition general formula of the scintillating ceramic is (Lu1‑x‑yCexMey)3Al5O12, the Me is Ca2+、Ba2+、Zn2+、Li+、Na+One kind or Ca in ion2+、Ba2+、Zn2+、Li+、Mg2+、Na+At least two in ion, wherein 0 ＜ x≤0.05,0 ＜ y≤0.1.This preparation method has simple for process, the advantages such as production cost is low, the LuAG of lower valency ion doping prepared:Ce, Me scintillating ceramic have stronger light emitting under ultraviolet or visible ray or the excitation of X rays or gamma-rays, and stimulated emission wavelength can be matched with the sensitizing range of photodetector, there is huge application potential in high-energy ray field of detecting.
Description
Technical field
(it is specially Ca the present invention relates to a kind of lower valency ion2+, Ba2+, Zn2+, Li+And Na+In one kind or their group
It closes or they and Mg2+Combination) doping LuAG:It Ce, Me twinkling transparent ceramics and preparation method thereof and is prepared by this method
Lower valency ion doping (Lu1-x-yCexMey)3Al5O12Twinkling transparent ceramics.Belong to the technology of light function crystalline ceramics preparation
Field.
Background technology
Scintillator refers to occur under radioactive ray or nuclear particle effect the photoelectric functional material of phosphere, conduct
The core element of beam energy detector, in high-energy physics, nuclear medical imaging (XCT and PET), industry CT on-line monitoring, oil well exploration,
The fields such as safety random check and anti-terrorism application have a wide range of applications.
With the rapid development of nuclear science technology and other the relevant technologies, the application field of inorganic scintillation material is not yet
Disconnected widens, conventional Flash crystal such as NaI:Or easily deliquescence, the low (3.67g/cm of density such as Tl, BGO3) or photoyield it is low
(only NaI:The 20-25% of Tl), die-away time longer (300ns), temperature stability it is poor, be difficult to meet many applications necks
Domain increasing performance requirement to scintillation material, exploring New Scintillators becomes currently or hereafter period material scholar's
Urgent task.In recent years, with Ce3+And Pr3+Luetcium aluminum garnet (LuAG), perovskite (LuAP) and silicic acid lutetium for active ions
(LSO) isostructural scintillation crystal and ceramics become the hot spot of concern and research both at home and abroad.Wherein, LuAG:Ce has relatively
High density (ρ=6.73g/cm3), high effective atomic number (Zeff=60), the fast die-away time of 50ns or so, 500-
The transmitting band of 550nm can and Si- photodiodes couple well and higher theoretical photoyield (60000ph/MeV) etc.
A kind of performance, it is considered to be the wide high-performance scintillation material of new generation of commercial promise.
2006, Liu Xuejian etc. proposed a kind of Luetcium aluminum garnet-base transparent ceramic and preparation method thereof
[CN1837142A], the structural formula which provides are Lu3-xRExAl5O12, 0<The rare earths such as x≤0.15, RE Ce, Pr are sent out
Photoion.It is characterized in that the nanoscale SiO that weight ratio is 0.1~1.0% is added in during ceramic system is standby2Or analysis is pure
Silester (TEOS) is as sintering aid.Shi Yun etc. proposes the twinkling transparent ceramics system and its system of a kind of garnet structure
Preparation Method [CN101514100B], the structural formula which provides are 3mR, 3nR '：(A1-m-n-xA’x)3(ByC1-y)5O12, 0≤m
≤ 0.1,0≤n≤0.1,0≤x≤1,0≤y≤0.4.It is characterized in that using Ce, Pr, Nd, Sm, Eu, Tb, Dy, Ho, Er,
One kind or combination in Tm, Yb, Ti, Cr, Mn passes through the sintering for adding that mass fraction is 0.01-2.0% as light emitting ionic
Auxiliary agent is to obtain the twinkling transparent ceramics of high transmittance.
Above work adds sintering aid to prepare the crystalline ceramics of high optical quality during ceramic system is standby, due to
There is some difference for the ionic radius and valence state of sintering aid ion and matrix ion, and the lattices such as distortion of lattice are easily introduced after addition
Defect.Therefore, the performance of the Luetcium aluminum garnet crystalline ceramics of preparation is there are certain limitation, so far, not yet in LuAG:Ce
Important breakthrough is obtained in the luminescent properties research of scintillating ceramic.
Siemens Medical Solutions USA Inc. combined U niversity of Tennessee in 2006
Research Fundation develop a kind of high-performance divalent Ca2+Ion doping LSO monocrystalline scintillation material [US 8,278,
624B2], and successfully push to be commercialized PET medical applications.
From the point of view of the present Research and progress of scintillation single crystal and scintillating ceramic, scintillating ceramic have preparation process it is simple, into
This is low, the advantages that producing large scale sample, high concentration Uniform Doped can be achieved and produce in enormous quantities, increasingly by people
Attention.A kind of remarkable in economical benefits is developed, the LuAG of high luminescence energy having a extensive future:Ce scintillating ceramics will have ten
Divide important meaning.
Invention content
In view of the above-mentioned problems, the purpose of the present invention is to provide a kind of LuAG of lower valency ion doping:Ce, Me flicker pottery
Porcelain and preparation method thereof.
On the one hand, the present invention provides a kind of LuAG of lower valency ion doping:Ce, Me scintillating ceramic, the flicker pottery
The composition general formula of porcelain is (Lu1-x-yCexMey)3Al5O12, the Me is Ca2+、Ba2+、Zn2+、Li+、Na+One kind in ion or
Ca2+、Ba2+、Zn2+、Li+、Mg2+、Na+At least two in ion, wherein 0 ＜ x≤0.05,0 ＜ y≤0.1.
With Ce in the present invention3+For active ions, using Me as Ca2+, Ba2+, Zn2+, Li+And/or Na+One kind in ion or
Combination thereof or they and Mg2+Be combined as Doped ions, a kind of LuAG of lower valency ion doping is prepared:Ce,
Me cubic garnet structure scintillating ceramics.Wherein, Lu in the ionic radius and matrix of the active ions and Doped ions3+From
Sub- radius is close, on this condition, the active ions Ce3+With Doped ions Me entering part Luetcium aluminum garnet structure cells, substitution
The Lu of Dodecahedral sites3+Ion.By charge compensation mechanism, (by taking divalent ion Me doping as an example, charge compensation mechanism isIn the scintillating ceramic system of preparation
Middle induction generates Ce4+Ion contains Ce simultaneously to maintain charge balance, so as to obtain3+And Ce4+The high-performance of light emitting ionic
LuAG:Ce, Me scintillating ceramic.
Preferably, the scintillating ceramic composition contains Ce simultaneously3+And Ce4+Two kinds of light emitting ionics.
Preferably, general formula (Lu1-x-yCexMey)3Al5O12In Ce3+For active ions, active ions Ce3+With Doped ions
Me enters Luetcium aluminum garnet structure cell, replaces the Lu of Dodecahedral sites3+Ion.
On the other hand, the present invention provides a kind of LuAG of lower valency ion doping:The preparation side of Ce, Me scintillating ceramic
Method, including：
LuAG is prepared according to stoichiometric ratio:The precursor powder of Ce, Me scintillating ceramic；
Gained precursor is body formed, obtain biscuit of ceramics；
By gained biscuit of ceramics through oversintering, annealing, the LuAG of the lower valency ion doping is obtained:Ce, Me flicker pottery
Porcelain.
Preferably, by Lu2O3、CeO2、Al2O3And the salt or oxide of co-dopant ions Me, according to (Lu1-x- yCexMey)3Al5O12Stoichiometric ratio weigh dispensing, by chemical raw material be configured mix, ball milling, dry, be sieved, obtain
Precursor powder.
Also, preferably, the salt or oxide of the co-dopant ions Me are Li2O、LiF、Li2CO3、LiOH·H2O、CaO、
BaO、ZnO、MgO、Na2At least one of O.
Also, preferably, the ball-milling medium of the ball milling is absolute ethyl alcohol, rotational speed of ball-mill is 60~150rmp/ minutes, ball milling
Time is 5~20 hours.
Preferably, by Al3+、Lu3+、Ce3+, Me solution is according to (Lu1-x-yCexMey)3Al5O12Stoichiometric ratio mixing, drop
Enter NH4OH or NH4HCO3, after ageing, washing, calcined 1~5 hour then at 600~1000 DEG C, obtain presoma powder.
Preferably, by Al3+、Lu3+、Ce3+, Me solution is according to (Lu1-x-yCexMey)3Al5O12Stoichiometric ratio mixing, with
Citric acid is complexing agent, and ethylene glycol is oxidant, obtains gel；
Gained gel at 800~1000 DEG C is calcined 2~10 hours, obtains presoma powder.
Also, preferably, the solution is contains Al respectively3+、Lu3+、Ce3+, Me soluble-salt, the soluble-salt is
At least one of nitrate, carbonate, sulfate.
Preferably, the molding mode of biscuit of ceramics adds isostatic cool pressing, colloidal formation, injection forming, gel injection-moulding for dry-pressing
Or electrophoretic deposition.
Preferably, the sintering processes are vacuum-sintering, HIP sintering or first hot pressing are burnt again after first vacuum-sintering
HIP sintering again after knot.
Also, preferably, the technological parameter of the vacuum-sintering is：Sintering temperature is 1700~1900 DEG C, and the time is 5~50
Hour；
The technological parameter of the HIP sintering is：1600~1850 DEG C, 100~200MPa of sintering pressure of sintering temperature is protected
Warm 1~4 hour time；
The technological parameter of the hot pressed sintering is：1700~1850 DEG C, 20~50MPa of sintering pressure of sintering temperature, soaking time 1
~8 hours.
Preferably, it is made annealing treatment 5~50 hours at 1200~1600 DEG C in oxidizing atmosphere.Using in oxygen-containing atmosphere
Long period annealing process so that Ce3+Ionic portions are oxidized to Ce4+Ion increases Ce4+Relative concentration, it is final obtain it is same
Shi Hanyou Ce3+And Ce4+The better scintillating ceramic of luminescent properties of two kinds of centres of luminescence.
Also, preferably, the oxidizing atmosphere is air atmosphere or/and oxygen atmosphere.
The present invention prepares presoma powder using solid reaction process or liquid phase method；The presoma powder is processed into
Type obtains biscuit of ceramics；Biscuit of ceramics is sintered, made annealing treatment and is machined successively, obtains required transparent sudden strain of a muscle
Bright ceramics.
This preparation method has simple for process, the advantages such as production cost is low, the LuAG of lower valency ion doping prepared:
Ce, Me scintillating ceramic have stronger light emitting, stimulated emission under ultraviolet or visible ray or X-ray or gamma-radiation excitation
Wavelength can be matched with the sensitizing range of photodetector, there is huge application potential in high-energy ray field of detecting.
Description of the drawings
Fig. 1 is the lower valency Li that a diameter of 15mm, thickness prepared by embodiment 1 is 1mm+The LuAG of ion doping:0.3%
The absorption spectrum of Ce, 0.1%Li scintillating ceramic；
Fig. 2 is LuAG prepared by embodiment 1:Excitation spectrum (the λ of 0.3%Ce, 0.1%Li scintillating ceramicem=512nm) and hair
Penetrate spectrum (λex=426nm)；
Fig. 3 is LuAG prepared by embodiment 1:The x-ray fluorescence emission spectrum of 0.3%Ce, 0.1%Li scintillating ceramic, it is commercial
BGO monocrystalline is standard sample；
Fig. 4 is LuAG prepared by embodiment 2:The photoyield of 0.3%Ce, 0.3%Li scintillating ceramic；
Fig. 5 is LuAG prepared by embodiment 2:The scintillation decay curve of 0.3%Ce, 0.3%Li scintillating ceramic；
Fig. 6 is ion of the Me ions under the conditions of four-coordination (tetrahedron), 6 coordinations (octahedron), 8 coordination (dodecahedron) cases
Radius；
Fig. 7 is LuAG prepared by embodiment 1:The XRD diagram of 0.3%Ce, 0.1%Li scintillating ceramic；
Fig. 8 is LuAG prepared by embodiment 2:LuAG prepared by 0.3%Ce, 0.3%Li scintillating ceramic, embodiment 3:0.3%Ce,
(Lu prepared by 0.1%Mg, 0.1%Li scintillating ceramic, comparative example 10.996Ce0.003Mg0.001)3Al5O12Scintillating ceramic and comparison
(Lu prepared by example 20.997Ce0.003)3Al5O12The photoyield of ceramics；
Fig. 9 is LuAG prepared by embodiment 2:LuAG prepared by 0.3%Ce, 0.3%Li scintillating ceramic, embodiment 3:0.3%Ce,
(Lu prepared by 0.1%Mg, 0.1%Li scintillating ceramic, comparative example 10.996Ce0.003Mg0.001)3Al5O12Scintillating ceramic and comparison
(Lu prepared by example 20.997Ce0.003)3Al5O12The scintillation decay curve of ceramics.
Specific embodiment
It is further illustrated the present invention below by way of following embodiments, it should be appreciated that following embodiments are merely to illustrate this
Invention, is not intended to limit the present invention.
The present invention prepares presoma powder using solid reaction process or liquid phase method, and then the presoma powder is added
Work is molded, and obtains biscuit of ceramics.Finally biscuit of ceramics is sintered, made annealing treatment and is machined successively, obtains lower valency
The LuAG of ion doping:Ce, Me scintillating ceramic.The composition general formula of the scintillating ceramic is：(Lu1-x-yCexMey)3Al5O12,
Ce3+For active ions, Doped ions Me is Ca2+, Ba2+, Zn2+, Li+And Na+One kind or combination thereof in ion or they
With Mg2+Combination.The value range of wherein x, y is respectively：0<X≤0.05,0<y≤0.1.Since the low price Me ions of doping are mixed
Miscellaneous effect, LuAG:The Ce of variable valency in Ce, Me ceramics3+Ion is Ce by portions turn4+To realize charge balance, thus it is described
Scintillating ceramic composition contains Ce simultaneously3+And Ce4+Two kinds of light emitting ionics.
Illustrate to following exemplary the LuAG of lower valency ion doping provided by the invention:The preparation of Ce, Me scintillating ceramic
Method.
Presoma powder is prepared using solid reaction process or liquid phase method.
Presoma powder is prepared by solid phase method.Concrete technology is：By the stoichiometric ratio (Lu1-x-yCexMey)3Al5O12Carry out weighing Al2O3, Lu2O3, CeO2Powder and one or more low price co-dopant ions Me (Ca2+, Ba2+, Zn2+, Mg2 +, Li+And/or Na+) salt or oxide raw material powder.The salt or oxide of the co-dopant ions Me can be Li2O、LiF、
Li2CO3、LiOH·H2O、CaO、BaO、ZnO、MgO、Na2At least one of O.The side that above-mentioned raw materials powder is passed through into wet ball grinding
Formula is uniformly mixed；The presoma powder is made in dry, sieving.Wherein ball-milling medium is absolute ethyl alcohol, and rotational speed of ball-mill can be 60-
150rmp/min, Ball-milling Time can be 5-20h.
Liquid phase method (wet chemistry method, including the precipitation method, sol-gal process, combustion synthesis method etc.) prepares presoma powder.Tool
Body technology：Corresponding Al is measured by the stoichiometric ratio3+、Lu3+、Ce3+With one or more of low price ion (Li+, Ca2+, Ba2 +, Zn2+, Mg2+And/or Na+) solution, directly synthesize to obtain using the liquid phase methods such as the precipitation method or sol-gel conbustion synthesis
Component is [Lu1-x-yCexMey]3Al5O12Initial powder (presoma powder).Solution described above is contains Al respectively3+、Lu3 +、Ce3+, Me soluble-salt, the soluble-salt can be nitrate, carbonate, at least one of sulfate.
By gained presoma powder be directly compressed into type or first precalcining processing (calcination temperature can be 400-1000 DEG C,
Time 2-10 hour) re-compacted molding afterwards, obtain ceramic institute.Wherein moulding process can be used dry-pressing add isostatic cool pressing, colloidal state into
Type, injection forming, gel injection-moulding or electrophoretic deposition etc..
By the biscuit of ceramics of compression moulding by sintering processes, the scintillating ceramic is obtained.Sintering processing can be that vacuum is burnt
Knot, vacuum-sintering is combined with HIP sintering, hot pressed sintering is combined with HIP sintering.The wherein technique of vacuum-sintering
Parameter can be：1700-1900 DEG C of sintering temperature, soaking time 5-50h.The technological parameter of HIP sintering can be：Sintering temperature
1600~1850 DEG C, 100~200MPa of sintering pressure of degree, soaking time 1~4 hour.The technological parameter of hot pressed sintering can be：It burns
1700~1850 DEG C, 20~50MPa of sintering pressure of junction temperature, soaking time 1~8 hour.
By the LuAG of the lower valency ion doping after sintering processes:Ce scintillating ceramics are made annealing treatment again.Wherein
Annealing atmosphere is air or/and oxidizing atmosphere.Annealing temperature can be 1200-1600 DEG C, and annealing soaking time can be 5-50h.More
Preferred annealing temperature can be 1350-1450 DEG C, and annealing soaking time preferably can be 10-20h.It so can fully eliminate material
Present in Lacking oxygen defect, and make part Ce3+It is oxidized to Ce4+, increase Ce4+Relative concentration.
It is finally that the ceramics sample after annealed process is as needed, then through mechanically polishing and processing, obtain required
The LuAG wanted:Ce, Me twinkling transparent ceramics.
The present invention is in the LuAG for preparing lower valency ion doping:It is preferred using raw material during Ce, Me scintillating ceramic：
The raw material of matrix and active ions：Commercial high-purity (more than 99.9% purity) α-Al2O3Or γ-Al2O3,Lu2O3With
CeO2Or its corresponding nitrate hydrate；
Matrix and active ions raw material：Wet chemistry method (including the precipitation method, sol-gal process, combustion synthesis method etc.) is prepared high-purity
(more than 99.9% purity) Al2O3、Lu2O3And CeO2Powder or nitrate solution；
Doped ions raw material：High-purity (more than 99.5% purity) Li may be selected in commercial Li raw materials2O, LiF, Li2CO3, LiOH
H2O powders；
Doped ions raw material：Commercial high-purity (more than 99.9% purity) CaO, BaO, ZnO, MgO and Na2O or corresponding nitric acid
Salt crystalline hydrate.
Heretofore described scintillating ceramic establishes the Lu in the ionic radius of Doped ions and matrix3+And active ions Ce3+
Ionic radius it is similar on the basis of, using the high pure raw material of the invention selection and the process conditions of offer, pass through charge compensation
Mechanism generates Ce in induction system4+Ion is annealed with maintaining charge balance in combination with the depth after sintering in oxygen-containing atmosphere
Technique contains Ce simultaneously so as to obtain3+And Ce4+The high-performance LuAG of light emitting ionic:Ce, Me scintillating ceramic.It is provided by the invention
Scintillating ceramic has density height, decays soon, to the absorbability of high-energy ray or particle (X-ray, gamma-radiation, α and β particles)
By force, high luminous efficiency and other features can be used as the Primary Component of scintillation detector, in high-energy physics (HEP), nuclear medicine
Fields such as (PET, CT) have huge application potential.
Embodiment is enumerated further below so that the present invention will be described in detail.It will similarly be understood that following embodiment is served only for this
Invention is further described, it is impossible to be interpreted as limiting the scope of the invention, those skilled in the art is according to this hair
Some nonessential modifications and adaptations that bright the above is made all belong to the scope of protection of the present invention.Following examples are specific
Technological parameter etc. is also only an example in OK range, i.e. those skilled in the art can be done properly by the explanation of this paper
In the range of select, and do not really want to be defined in hereafter exemplary concrete numerical value.
Embodiment 1 x=0.003, y=0.001, (Lu0.996Ce0.003Li0.001)3Al5O12
Active ions Ce3+A concentration of 0.3at.%, low price Li+Doping concentration is 0.1at.%.It is by commercially available purity
99.99% Lu2O3, Al2O3, CeO2And LiOHH2O material powders stoichiometrically (Lu0.996Ce0.003Li0.001)3Al5O12Weigh, ball-milling medium made using absolute ethyl alcohol, with 80rmp/min rotational speed of ball-mill on high energy ball mill ball milling 10h.It will
After slurry drying and screening after ball milling, biscuit of ceramics is obtained by dry-pressing formed and cold isostatic compaction successively, biscuit is in vacuum
It is sintered in stove, sintering temperature is 1750 DEG C, and the time is 20 hours.The ceramics sample that vacuum-sintering obtains passes through 1400 DEG C of air gas
After atmosphere annealing 8h, mechanical reduction and polishing treatment are carried out, obtains a diameter of 15mm, thickness is the fine and close transparent LuAG of 1mm:
0.3%Ce, 0.1%Li twinkling transparent ceramics.
Embodiment 2 x=0.003, y=0.003, (Lu0.994Ce0.003Li0.003)3Al5O12
Active ions Ce3+A concentration of 0.3at.%, low price Li+Doping concentration is 0.3at.%.It is by commercially available purity
99.99% Lu2O3, Al2O3, CeO2And LiOHH2O material powders stoichiometrically (Lu0.994Ce0.003Li0.003)3Al5O12Weigh, ball-milling medium made using absolute ethyl alcohol, with 120rmp/min rotational speed of ball-mill on high energy ball mill ball milling 8h.It will
After slurry drying and screening after ball milling, biscuit of ceramics is obtained by dry-pressing formed and cold isostatic compaction successively, biscuit is in vacuum
It is sintered in stove, sintering temperature is 1880 DEG C, and the time is 30 hours.The ceramics sample that vacuum-sintering obtains passes through 1500 DEG C of air gas
After atmosphere annealing 12h, mechanical reduction and polishing treatment are carried out, obtains a diameter of 15mm, thickness is the fine and close transparent of 1mm
LuAG:0.3%Ce, 0.3%Li twinkling transparent ceramics.
Embodiment 3 x=0.003, y=0.002, (Lu0.995Ce0.003Li0.001Mg0.001)3Al5O12
Active ions Ce3+A concentration of 0.3at.%, the concentration of low price Li and Mg combined dopants be respectively 0.05at.% and
0.1at.%.By the Lu that commercially available purity is 99.99%2O3, Al2O3, CeO2, MgO and Li2O material powders are pressed
(Lu0.995Ce0.003Li0.001Mg0.001)3Al5O12Chemical formula weigh, ball-milling medium is made using absolute ethyl alcohol, with 100rmp/min
Rotational speed of ball-mill ball milling 15h on high energy ball mill.After the slurry drying and screening after ball milling, successively by dry-pressing formed and cold etc.
Hydrostatic profile obtains biscuit of ceramics, and biscuit is sintered in a vacuum furnace, and sintering temperature is 1850 DEG C, and the time is 20 hours.Vacuum is burnt
It ties obtained ceramics sample to anneal in the mixing of oxygen and air 20h, 1500 DEG C of annealing region, finally through mechanical reduction
And polishing treatment, obtain a diameter of 15mm, the fine and close transparent LuAG that thickness is 1mm:0.3%Ce, 0.1%Mg, 0.1%Li dodge
Bright crystalline ceramics.
Embodiment 4 x=0.005, y=0.01, (Lu0.985Ce0.005Ca0.01)3Al5O12
Active ions Ce3+A concentration of 0.5at.%, low price Ca2+Doping concentration is 1at.%.Using commercially available high-purity Lu2O3,
Al2O3, CeO2CaO powders are raw material, and each oxide and hydrate powder first are dissolved in nitric acid and are configured to nitrate solution.It is or straight
It connects using commercially available Lu (NO3)3, Al (NO3)3, Ce (NO3)3With Ca (NO3)2Salt is raw material.Using citric acid as complexing agent, ethylene glycol
For oxidant, ceramic forerunner powder is prepared using collosol and gel-combustion synthesis method.Concrete technology is to press
(Lu0.985Ce0.005Ca0.01)3Al5O12Chemical formula weigh Lu (NO3)3, Al (NO3)3, Ce (NO3)3With Ca (NO3)2Solution and
Citric acid, the additive amount molar ratio of metal ion and citric acid is 1 here:2.Heating stirring is extremely in magnetic stirring apparatus or water-bath
Citric acid dissolves and it is made fully to be chelated with ionizable metal salt.It adds a certain amount of ethylene glycol to stir to colloidal sol is formed, here lemon
The additive amount molar ratio of lemon acid and ethylene glycol is 1:3.Heating temperature is increased again and continues to stir, until forming clear viscous
Gel.Raising temperature is continued thereafter with, combustion reaction occurs for gel, and yellowish-brown of emerging smog obtains fluffy forerunner after reaction
Body.Finally by precursor powder in 600-1000 DEG C of temperature range calcination processing, you can obtain LuAG:0.5%Ce, 1%Ca
Precursor powder.After above-mentioned precursor powder is sieved, biscuit of ceramics is obtained by dry-pressing formed and cold isostatic compaction successively, element
Base is sintered in a vacuum furnace, and sintering temperature is 1720 DEG C, and the time is 50 hours.The ceramics sample that vacuum-sintering obtains passes through 1300
After DEG C air atmosphere annealing 40h, mechanical reduction and polishing treatment are carried out, obtains a diameter of 15mm, the densification that thickness is 1mm
Transparent LuAG:0.5%Ce, 1%Ca twinkling transparent ceramics.
Embodiment 5 x=0.01, y=0.02, (Lu0.97Ce0.01Zn0.02)3Al5O12
Active ions Ce3+A concentration of 1at.%, low price Zn2+Doping concentration is 2at.%.It is 99.99% by commercially available purity
Lu2O3, Al2O3, CeO2With ZnO material powders stoichiometrically (Lu0.97Ce0.01Zn0.02)3Al5O12It weighs, use is anhydrous
Ethyl alcohol makees ball-milling medium, with 60-120rmp/min rotational speed of ball-mill on high energy ball mill ball milling 10-20h.By the slurry after ball milling
After drying and screening, biscuit of ceramics is obtained by dry-pressing formed and cold isostatic compaction successively, biscuit is in 1760 DEG C of temperature ranges
Vacuum-sintering.Sintering temperature is 30 DEG C, and the time is 20 hours.The ceramics sample that vacuum-sintering obtains passes through 1350 DEG C of air atmospheres
After making annealing treatment 20h, mechanical reduction and polishing treatment are carried out, obtains a diameter of 15mm, thickness is the fine and close transparent of 1mm
LuAG:1%Ce, 2%Zn twinkling transparent ceramics.
A diameter of 15mm, the lower valency Li that thickness is 1mm that Fig. 1 is prepared by embodiment 1+The LuAG of ion doping:0.3%
The absorption spectrum of Ce, 0.1%Li scintillating ceramic shows to contain Ce simultaneously in prepared sample3+And Ce4+Light emitting ionic.Due to sample
Product thickness and instrument reason, Ce in Fig. 13+Absorption of the ion at 347nm and 450nm reaches saturation.
Fig. 2 presses LuAG prepared by embodiment 1:Excitation spectrum (the λ of 0.3%Ce, 0.1%Li scintillating ceramicem=512nm) and
Emission spectrum (λex=426nm).Abscissa is wavelength, and ordinate is luminous intensity.The glow peak of prepared sample is in 512nm
Place, within the highly sensitive detecting area of silicon photodetector.
Fig. 3 presses LuAG prepared by embodiment 1:The x-ray fluorescence emission spectrum of 0.3%Ce, 0.1%Li scintillating ceramic, quotient
It is standard sample with BGO monocrystalline.Abscissa is wavelength, and ordinate is luminous intensity.Show compared with BGO monocrystalline, prepared pottery
Porcelain has very strong luminous efficiency.
Fig. 4 presses LuAG prepared by embodiment 2:The photoyield of 0.3%Ce, 0.3%Li scintillating ceramic shows in 1 μ s-10 μ s
Test gate-width under, photoyield is superior to be not added with the LuAG of Li:0.3%Ce ceramics, and at the same time the LuAG better than same component:
0.3%Ce monocrystalline illustrates that the addition of Li plays an important roll the photoyield for improving material.
Fig. 5 presses LuAG prepared by embodiment 2:The scintillation decay curve of 0.3%Ce, 0.3%Li scintillating ceramic, shows its tool
There is fast decay of luminescence, attenuation characteristic is excellent similary better than the LuAG for not mixing Li:0.3%Ce and corresponding monocrystalline.
Fig. 7 is the LuAG prepared by embodiment 1:The XRD diagram of 0.3%Ce, 0.1%Li scintillating ceramic shows the pottery prepared
Porcelain is single LuAG cubic phase, and Ce and Doped ions Li can preferably dissolve in lattice.
Fig. 8 presses LuAG prepared by embodiment 2:LuAG prepared by 0.3%Ce, 0.3%Li scintillating ceramic, embodiment 3:
(Lu prepared by 0.3%Ce, 0.1%Mg, 0.1%Li scintillating ceramic, comparative example 10.996Ce0.003Mg0.001)3Al5O12Scintillating ceramic
And (Lu prepared by comparative example 20.997Ce0.003)3Al5O12The photoyield of ceramics, shows under the test gate-width of 1 μ s-10 μ s,
Photoyield is superior to be not added with the LuAG of Li and Mg:0.3%Ce ceramics illustrate that the addition of Li and Mg has the photoyield for improving material
It plays an important role.In addition, it is added to the LuAG of Li:Ce, Li scintillating ceramic and LuAG:Ce, Mg, Li scintillating ceramic are in test gate-width
Photoyield when larger is above only adding the LuAG of Mg:Ce, Mg scintillating ceramic.
Fig. 9 presses LuAG prepared by embodiment 2:LuAG prepared by 0.3%Ce, 0.3%Li scintillating ceramic, embodiment 3:
(Lu prepared by 0.3%Ce, 0.1%Mg, 0.1%Li scintillating ceramic, comparative example 10.996Ce0.003Mg0.001)3Al5O12Scintillating ceramic
And (Lu prepared by comparative example 20.997Ce0.003)3Al5O12The scintillation decay curve of ceramics, shows that its attenuation characteristic is equally better than
The LuAG of Li and Mg are not mixed:0.3%Ce ceramics.In addition, it is added to the LuAG of Li:Ce, Li scintillating ceramic and LuAG:Ce,Mg,Li
The die-away time of scintillating ceramic is better than the LuAG for only adding Mg:Ce, Mg scintillating ceramic, but its fast emission component is less than the latter.
Comparative example 1 x=0.003, y=0.001, (Lu0.996Ce0.003Mg0.001)3Al5O12
Active ions Ce3+A concentration of 0.3at.%, a concentration of 0.1at.% of low price Mg combined dopants.By commercially available purity
For 99.99% Lu2O3, Al2O3, CeO2, MgO material powders are by (Lu0.9955Ce0.003Li0.0005Mg0.001)3Al5O12Chemistry
Formula weighs, and makees ball-milling medium using absolute ethyl alcohol, with 100rmp/min rotational speed of ball-mill on high energy ball mill ball milling 15h.By ball
After slurry drying and screening after mill, biscuit of ceramics is obtained by dry-pressing formed and cold isostatic compaction successively, biscuit is in vacuum drying oven
Middle sintering, sintering temperature are 1850 DEG C, and the time is 20 hours.The ceramics sample that vacuum-sintering obtains is in the mixing of oxygen and air
Middle annealing 20h, 1450 DEG C of annealing region finally through mechanical reduction and polishing treatment, obtain a diameter of 15mm, thickness is
The fine and close transparent LuAG of 1mm:0.3%Ce, 0.1%Mg twinkling transparent ceramics.
Comparative example 2 x=0.003, y=0.000, (Lu0.997Ce0.003)3Al5O12
Active ions Ce3+A concentration of 0.3at.%, low price Li+Doping concentration is 0.3at.%.It is by commercially available purity
99.99% Lu2O3, Al2O3, CeO2And LiOHH2O material powders stoichiometrically (Lu0.997Ce0.003)3Al5O12It weighs,
Ball-milling medium is made using absolute ethyl alcohol, with 120rmp/min rotational speed of ball-mill on high energy ball mill ball milling 8h.By the slurry after ball milling
After expecting drying and screening, biscuit of ceramics is obtained by dry-pressing formed and cold isostatic compaction successively, biscuit is sintered in a vacuum furnace, is burnt
Junction temperature is 1880 DEG C, and the time is 30 hours.The ceramics sample that vacuum-sintering obtains makes annealing treatment by 1450 DEG C of air atmospheres
After 20h, mechanical reduction and polishing treatment are carried out, obtains a diameter of 15mm, the fine and close transparent LuAG that thickness is 1mm:0.3%Ce
Twinkling transparent ceramics (LuAg:Ce).
Claims (10)
1. a kind of LuAG of lower valency ion doping:Ce, Me scintillating ceramic, which is characterized in that the composition of the scintillating ceramic leads to
Formula is (Lu1-x-yCexMey)3Al5O12, the Me is Ca2+、Ba2+、Zn2+、Li+、Na+One kind or Ca in ion2+、Ba2+、Zn2 +、Li+、Mg2+、Na+At least two in ion, wherein 0 ＜ x≤0.05,0 ＜ y≤0.1.
2. according to the LuAG of lower valency ion doping as described in claim 1:Ce, Me scintillating ceramic, which is characterized in that described
Scintillating ceramic composition contains Ce simultaneously3+And Ce4+Two kinds of light emitting ionics.
3. according to the LuAG of lower valency ion doping as claimed in claim 1 or 2:Ce, Me scintillating ceramic, which is characterized in that
General formula (Lu1-x-yCexMey)3Al5O12In Ce3+For active ions, active ions Ce3+Enter lutetium aluminum pomegranate with Doped ions Me
Stone structure cell replaces the Lu of Dodecahedral sites3+Ion.
4. a kind of LuAG of the lower valency ion doping as described in any one of claim 1-3:The preparation side of Ce, Me scintillating ceramic
Method, which is characterized in that including：
LuAG is prepared according to stoichiometric ratio:The precursor powder of Ce, Me scintillating ceramic；
Gained precursor is body formed, obtain biscuit of ceramics；
By gained biscuit of ceramics through oversintering, annealing, the LuAG of the lower valency ion doping is obtained:Ce, Me flicker pottery
Porcelain.
5. preparation method according to claim 4, which is characterized in that by Lu2O3、CeO2、Al2O3And co-dopant ions
The salt or oxide of Me, according to (Lu1-x-yCexMey)3Al5O12Stoichiometric ratio weigh dispensing, the chemical raw material that will be configured
Mixing, ball milling is dry, sieving, obtains precursor powder, the salt or oxide of the co-dopant ions Me are Li2O、LiF、
Li2CO3、LiOH∙H2O、CaO、BaO、ZnO、MgO、Na2At least one of O.
6. preparation method according to claim 4 or 5, which is characterized in that by Al3+、Lu3+、Ce3+, Me solution according to
(Lu1-x-yCexMey)3Al5O12Stoichiometric ratio mixing, instill NH4OH or NH4HCO3, after ageing, washing, then at 600~
1000 DEG C are calcined 1~5 hour, obtain presoma powder.
7. according to the preparation method described in any one of claim 4-6, which is characterized in that by Al3+、Lu3+、Ce3+, Me solution
According to (Lu1-x-yCexMey)3Al5O12Stoichiometric ratio mixing, using citric acid as complexing agent, ethylene glycol is oxidant, is coagulated
Glue；
Gained gel at 800~1000 DEG C is calcined 2~10 hours, obtains presoma powder.
8. the preparation method described according to claim 6 or 7, which is characterized in that the solution is contains Al respectively3+、Lu3+、Ce3 +, Me soluble-salt, the soluble-salt is nitrate, carbonate, at least one of sulfate.
9. according to the preparation method described in any one of claim 4-8, which is characterized in that
The sintering processes are vacuum-sintering, reheating etc. after HIP sintering or first hot pressed sintering again after first vacuum-sintering
Static pressure is sintered；
The technological parameter of the vacuum-sintering is：Sintering temperature is 1700~1900 DEG C, and the time is 5~50 hours；
The technological parameter of the HIP sintering is：1600~1850 DEG C, 100~200MPa of sintering pressure of sintering temperature is protected
Warm 1~4 hour time；
The technological parameter of the hot pressed sintering is：1700~1850 DEG C, 20~50MPa of sintering pressure of sintering temperature, soaking time 1
~8 hours.
10. according to the preparation method described in any one of claim 4-9, which is characterized in that in oxidizing atmosphere 1200~
It is made annealing treatment 5~50 hours at 1600 DEG C.
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