CN101376520B - Method for preparing Ce3+ doped lutetium oxyorthosilicate luminescent powder using organic compound auxiliary low temperature - Google Patents
Method for preparing Ce3+ doped lutetium oxyorthosilicate luminescent powder using organic compound auxiliary low temperature Download PDFInfo
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- CN101376520B CN101376520B CN2008102002909A CN200810200290A CN101376520B CN 101376520 B CN101376520 B CN 101376520B CN 2008102002909 A CN2008102002909 A CN 2008102002909A CN 200810200290 A CN200810200290 A CN 200810200290A CN 101376520 B CN101376520 B CN 101376520B
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Abstract
The invention relates to a method for preparing Ce<3+> doped lutetium orthosilicate luminescent powders at low temperature by adopting an organic compound, which belongs to the preparation process technology field of rare earth compound luminescent powders. The method is characterized in that lutecium trichloride (LuCl3) and ethyl orthosilicate (TEOS) are used as raw materials, propylene oxide (PPO) is used as a reaction promoter, a pioneer precipitate is obtained through a proper liquid phase reaction, the calcination treatment is conducted subsequently at the temperature ranging from 900 to1300, the pioneer precipitate is processed through thermal retardation form 2 to 6 hours at the temperature ranging from 900 to 1300, and the Ce<3plus> doped lutetium orthosilicate luminescent powdersare obtained finally. The grain diameter of the obtained powders is about 200 nanometers, the particles are distributed evenly, and no agglomeration exists on the whole. In the method, single-phase lutetium orthosilicate (LSO) powders are obtained after calcining for 2 hours at lower temperature that is lower than 1000 DEG C. By adopting the method, the prepared Ce:LSO luminescent powders can beused in the growth of scintillation crystal in a scintillator detector, can be used in the preparation of scintillating ceramic material, and also can be used as luminescent powders singly.
Description
Technical field
The present invention relates to a kind of employing organic compound auxiliary low temperature and prepare Ce
3+The method of doped lutetium oxyorthosilicate luminescent powder belongs to rare earth compound luminescent powder fabricating technology field.
Background technology
C.L.Melcher in 1992 and J.S.Schweitzer two people find Lu first
2SiO
5(LSO:Ce) monocrystal material is a kind of scintillator material of superior performance, and its density is 7.4g/cm
3, effective atomic number is 66, and radiation length is 1.14cm, and emissive porwer is 75% of a thallium doped sodium iodide, and light is output as 26300ph/Mev, and be 40ns fall time, and energy resolution is 9%,, and emission peak is in 420nm.Based on above characteristics, this kind material is at CT (computerized tomography, Computed Tomography), and position emissron tomography technology nuclear imaging of medical technical elements such as (PET:Positron Emission Tomography) has wide application prospect.The research of cerium doping silicic acid lutetium scintillation single crystal has obtained huge progress, also faces problems simultaneously, and wherein comparatively serious problem is exactly the preparation of high quality LSO monocrystalline.Traditional single crystal preparation technology (Czochralski method) though can the superior scintillator crystals of obtained performance,, 2100 ℃ growth temperature and the pulling rate of 2mm/h not only experimental installation is proposed high requirement, and the production cycle are longer.In addition, the segregation coefficient of Ce in melt also limited Ce
3+Uniform distribution in large size LSO monocrystalline.For overcoming the above problems, we consider to adopt polycrystalline ceramics preparation technology to develop the adulterated silicic acid lutetium flicker of cerium polycrystalline bulk material.The most significant problems that this thinking need solve is the acquisition of nano-scale high reactivity polycrystalline silicic acid lutetium powder, because the powder of higher sintering activity is easy to prepare the polycrystalline material near theoretical density in follow-up densification sintering process.Nanoparticle has higher sintering activity because of its distinctive performance, so we wish to prepare nano level polycrystalline silicic acid lutetium powder under lower synthesis temperature.
From existing bibliographical information, the synthesis temperature of LSO material is very high, and often comprises more impurity phase in the synthetic product.Just can synthesize LSO phase powder as solid phase method at 1400～1500 ℃, Hayet Farhi is a raw material with lutecium oxide powder and airsetting silicon-dioxide, and compressing tablet behind the uniform mixing obtained the silicic acid lutetium powder of pure phase in 100 hours 1400 ℃ of annealing.It is serious that 1400 ℃ calcining temperature causes crystal grain to be reunited, and particulate is active significantly to be reduced, and seriously restricts finishing of follow-up densification process.Can impel uniform mixing between the reactant element based on the sol-gel method of hydrolysis of alkoxide, therefore the synthesis temperature of material also is reduced to 1200 ℃, picture C.Mansuy uses lutecium chloride, the alkoxide of potassium and TEOS are that raw material passes through Sol-gel technology acquisition LSO precursor, make silicic acid lutetium powder through 1200 ℃ of calcinings after 6 hours.But it is comparatively harsh that the problem of this sol-gel method is exactly a reaction conditions, very sensitive to aqueous vapor, general requirement is carried out under vacuum condition or exsiccant nitrogen atmosphere, and preparation cycle is long, picture ERICBESCHER uses metal Lu, Virahol and TEOS to be starting raw material, with mercury chloride is catalyzer, refluxes can obtain colloidal sol in 3～5 days in vacuum environment.
Summary of the invention
The purpose of this invention is to provide a kind of employing organic compound auxiliary low temperature and prepare Ce
3+The method of doped lutetium oxyorthosilicate luminescent powder.
A kind of employing organic compound auxiliary low temperature of the present invention prepares Ce
3+The method of doped lutetium oxyorthosilicate luminescent powder is characterized in that it being that following process and step are arranged:
A. Ce is determined in design
3+The chemical molecular formula of doping silicic acid lutetium:
(Lu
1-xCe
x)
2SiO
5, wherein, x is the molar content of rare earth doped Ce, x=0.001-0.05;
B. be dissolved in lutecium chloride powder and tetraethoxy (TEOS) in an amount of Virahol in 2: 1 in molar ratio, mixing solutions being stirred the add-on that adds reaction promoter propylene oxide (PPO) propylene oxide after 10-60 minute is benchmark by the molar mass of Lu, and promptly both ratio is: PPO: Lu=20: 1; Add a small amount of cerous nitrate subsequently, the add-on of cerous nitrate is calculated by above-mentioned chemical formula, i.e. Lu
3+: Ce
3+=(1-x): x, x=0.001-0.05; Under closed environment, reaction obtained the oyster white gelatinous precipitate after 6-30 hour under the magnetic agitation with mixing solutions; It both had been forerunner's throw out;
C. above-mentioned forerunner's throw out is placed under the air atmosphere 60-100 ℃ dry 5-20 hour, under 900-1300 ℃, carry out calcination processing then, and insulation 2-6 hour under this temperature; Temperature rise rate is 1-5 ℃/minute; Finally obtain Ce
3+Doping silicic acid luminescent powder.
Characteristics among the present invention are to adopt lutecium chloride (LuCl
3) and tetraethoxy (TEOS) be raw material, in the liquid-phase system of preparation silicic acid lutetium powder presoma, introduce propylene oxide (PPO) as reaction promoter, propylene oxide has certain chemical property: the oxygen with lone-pair electron in the propylene oxide attracts the proton hydrogen in the solution, and under the effect of reinforcing yin essence ionic, realize ring-opening reaction, realize that finally the pH value of solution slowly improves.
Cardinal principle in the inventive method can be expressed as follows: the proton hydrogen bond that hydrolytic dissociation goes out in propylene oxide and the reaction soln and, and open loop under the effect of the chlorion that lutecium chloride dissociates out, the pH value of solution slowly raises thus, resultant is exactly Lu hydroxylation slowly, and at the orthosilicic acid that tetraethoxy (TEOS) hydrolysis produces can condensation reaction take place immediately with the hydroxyl Lu that has just generated, finally can obtain the homogeneous gel system.
The action-reaction formula of propylene oxide (PPO) is as follows:
Wherein, M is Lu, and N is Cl.
The advantage of the inventive method is as follows:
(1). by adopting propylene oxide (PPO), guaranteed that rare earth atom Lu can more carry out uniform mixing with elements Si in the small scale scope as reaction promoter.
(2). its size distribution of the powder that the inventive method obtains is even, and size is 100-200nm, and particle diameter does not have reunion substantially; The inventive method can obtain the nano level silicic acid lutetium powder of pure phase in 2 hours at 1000 ℃ of temperature lower calcinations; Compare with solid phase method, the synthesis temperature of silicic acid lutetium has reduced about 400 ℃; Compare with sol-gel method, synthesis temperature has reduced by 200 ℃.
Description of drawings
Fig. 1 is the sedimentary scanning electron microscope of gained forerunner (SEM) shape appearance figure in the inventive method,
Fig. 2 is that the inventive method gained forerunner throw out is calcined X-ray diffraction (XRD) spectrogram after 2 hours under differing temps.
Fig. 3 is scanning electron microscope (SEM) shape appearance figure of forerunner's throw out at silicic acid lutetium (LSO) luminescent powder of 1000 ℃ of calcinings acquisition in 2 hours.Wherein (a) is the low power shape appearance figure, (b) is the high power shape appearance figure.
Fig. 4 is TEM pattern (a) and the HTEM pattern (b) of forerunner's throw out at silicic acid lutetium (LSO) powder of 1000 ℃ of calcinings acquisition in 2 hours.
The nano Ce that Fig. 5 makes for the present invention
3+The excitation spectrum and the emmission spectrum of doping silicic acid lutetium powder.
Embodiment
Now details are as follows with specific embodiments of the invention.
Embodiment 1
Lutecium chloride (LuCl with 20g
3), 8.05ml tetraethoxy (TEOS) (content of silicon-dioxide is 28.4%) be dissolved in the Virahol of 20ml, under 600 rev/mins of rotating speeds, stirred 30 minutes, the reaction promoter propylene oxide (PPO) and the 0.68ml concentration that add 99.61ml concentration subsequently and be 14.26mol/l are the cerous nitrate solution of 0.522mol/l, magnetic agitation is 24 hours in closed environment, stir speed (S.S.) is 1800 rev/mins, and reaction finishes the back and obtains white gels shape throw out, both has been forerunner's throw out.Forerunner's throw out is placed in 100 ℃ of following dryings in retort furnace, under 1000 ℃, carries out calcination processing in the alumina crucible, and insulation 2 hours under this temperature, temperature rise rate is 1.5 ℃/min, finally obtains Ce
3+Doped lutetium oxyorthosilicate luminescent powder.
Embodiment 2
Lutecium chloride (LuCl with 8g
3), 3.22ml tetraethoxy (TEOS) (content of silicon-dioxide is 28.4%) be dissolved in the Virahol of 10ml, under 600 rev/mins of rotating speeds, stirred 30 minutes, the reaction promoter propylene oxide (PPO) and the 0.27ml concentration that add 39.84ml concentration subsequently and be 14.26mol/l are the cerous nitrate solution of 0.522mol/l, magnetic agitation is 24 hours in closed environment, stir speed (S.S.) is 1800 rev/mins, and reaction finishes the back and obtains white gels shape throw out, both has been forerunner's throw out.Forerunner's throw out is placed in 100 ℃ of following dryings in retort furnace, under 1000 ℃, carries out calcination processing in the alumina crucible, and insulation 2 hours under this temperature, temperature rise rate is 1.5 ℃/min, finally obtains Ce
3+Doped lutetium oxyorthosilicate luminescent powder.
The powder sample of gained is listed in accompanying drawing through the result of every instrument detecting in the embodiment of the invention.
Fig. 1 is the sedimentary scanning electron microscope of gained forerunner (SEM) shape appearance figure in the present embodiment.
Fig. 2 is that gained forerunner throw out is calcined X-ray diffraction (XRD) collection of illustrative plates after 2 hours in the present embodiment under differing temps.As seen, its diffraction peak is all corresponding with single-phase silicic acid lutetium PDF card (41-0239) among the figure, and the diffraction peak of dephasign does not almost have.Explanation thus uses the inventive method can synthesize the silicic acid lutetium luminescent powder of pure phase in lower temperature.
Fig. 3 is scanning electron microscope (SEM) the appearance figure of the silicic acid lutetium luminescent powder that gained forerunner throw out obtained 1000 ℃ of calcinings in 2 hours in the present embodiment.As seen from the figure, the single particle size of silicic acid lutetium powder is about 100nm, and the single particle size distribution is even, does not have serious agglomeration.
Fig. 4 is that gained forerunner throw out is schemed at the TEM pattern (a) and the HRTEM pattern (b) of the silicic acid lutetium powder of 1000 ℃ of calcinings acquisition in 2 hours in the present embodiment.
Fig. 5 is the nano Ce of gained in the present embodiment
3+The excitation spectrum and the emmission spectrum of doping silicic acid lutetium powder.
The prepared Ce:LSO luminescent powder of the inventive method can be used for the growth of the scintillation crystal of scintillator detector, can be used for the preparation of flickering ceramic material, also can be used alone as luminescent powder.
Claims (1)
1. one kind is adopted organic compound low temperature to prepare Ce
3+The method of doped lutetium oxyorthosilicate luminescent powder is characterized in that it being that following process and step are arranged:
A. Ce is determined in design
3+The chemical molecular formula of doping silicic acid lutetium:
(Lu
1-xCe
x)
2SiO
5, wherein, x is the molar content of rare earth doped Ce, x=0.001-0.05;
B. be dissolved in lutecium chloride powder and tetraethoxy in an amount of Virahol in 2: 1 in molar ratio, mixing solutions stirred add the reaction promoter propylene oxide after 10-60 minute, the add-on of propylene oxide is a benchmark by the molar content of Lu, and promptly both ratio is: PPO: Lu=20: 1; Add a small amount of cerous nitrate subsequently, the add-on of cerous nitrate is calculated by above-mentioned chemical formula, i.e. Lu
3+: Ce
3+=(1-x): x, x=0.001-0.05; Under closed environment, reaction obtained the oyster white gelatinous precipitate after 6-30 hour under the magnetic agitation with mixing solutions; It both had been forerunner's throw out;
C. above-mentioned forerunner's throw out is placed under the air atmosphere 60-100 ℃ dry 5-20 hour, under 900-1300 ℃, carry out calcination processing then, and insulation 2-6 hour under this temperature; Temperature rise rate is 1-5 ℃/minute; Finally obtain Ce
3+Doped polycrystalline silicic acid lutetium luminescent powder.
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| CN101993240B (en) * | 2010-11-09 | 2013-03-06 | 上海大学 | Preparation method of Ce3+doped lutetium silicate (Lu2SiO5) polycrystalline flashing optical ceramic |
| CN102391868B (en) * | 2011-09-15 | 2013-03-06 | 上海大学 | Preparation method of cerium ion-doped lutetium silicate powder by liquid phase package method at low temperature |
| CN102690113A (en) * | 2012-06-06 | 2012-09-26 | 上海大学 | Method for preparing Ce:Lu3Al5O12 transparent ceramic scintillator by low-temperature vacuum sintering |
| CN105176531A (en) * | 2015-05-21 | 2015-12-23 | 上海大学 | Cerium doped lutetium silicate spherical luminescent powder and preparation method thereof |
| CN111017982B (en) * | 2019-12-31 | 2022-02-01 | 中南大学 | Nano-grade rare earth silicate powder material and application thereof |
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