CN101949061B - Rare earth-doped lutetium-scandium borate scintillation single crystals and growth method thereof - Google Patents
Rare earth-doped lutetium-scandium borate scintillation single crystals and growth method thereof Download PDFInfo
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Abstract
The invention relates to the technical field of inorganic compound crystals and manufacturing, and provides a float-zone growth method of rare earth-doped lutetium-scandium borate single crystals. The rare earth-doped lutetium-scandium borate single crystals with high crystal quality are obtained by successfully utilizing the float-zone method, wherein the single crystals have the structural formula of (Lu1-xScx)1-yMyBO3; x is greater than or equal to 0.1 and less than or equal to 0.7; y is greater than 0 and less than or equal to 0.1; and M represents one or more of Ce, Pr, Eu, Tb and Yb. The method provided by the invention comprises the four steps of synthesis, melting, inoculation, growing and cooling. Compared with a crystal pulling method, the method has the advantages of high efficiency, low cost, low energy consumption and the like.
Description
Technical field
The present invention relates to a kind of inorganic compound crystal and manufacturing technology field, particularly relate to a kind of growth method of rear-earth-doped boric acid lutetium scandium scintillation single crystal.
Background technology
(chemical formula is LuBO to the boric acid lutetium
3) crystal is a kind of scintillation crystal of finding recently, it has, and physical and chemical performance is good, and transparency range is wide, thereby it is particularly suitable for doing the matrix of Ce ion doping excellent performance scintillation crystal.In the scintillator international conference (Scint ' 95) of nineteen ninety-five, the scientist MJ.Weber of U.S. LBNL [MJ.Weber, S.E.Derenzo, C.DuJardin, et al.Dense Ce
3+-activated scintillator materials, Proceedings of Scint ' 95, pp.325-328, (Edited by P.Dorenbos and C.W.E.vanEijk) Delft, The Netherlands, 1996] pass through a series of high-density Ce
3+Point out LuBO after the research of adulterated powder material scintillation properties
3: Ce is a kind of promising novel high-performance scintillation material.U.S. scientist William Moses [W.W.Moses afterwards; Et al.Recent results in a search for inorganicscintillators for X-and gamma ray detection; In:Proceedings of Scint ' 97; 1997, p.358], Lyons, France first L.Zhang of university [L.Zhang, the C.Pedrini; C.Madej; Et al.Fast fluorescence and scintillationproperties of cerium and praseodymium doped lutetium orthoborates.Radiation Effects andDefects in Solids, 150, (1999) 47-52] etc. the people all further confirmed the scintillation properties that it is superior through the powder experiment.But up to the present never have LuBO
3: the relevant report of Ce single crystal performance, and have only LuBO
3: the report of Ce powder body material performance; And the performance of its powder is compared still to have obviously with other scintillation crystal and is had superiority; And in the powder owing to have a large amount of crystal boundaries, macroscopic view or microdefect, thereby generally speaking its performance can be poorer than the single crystal material with component.Practice in the past and theoretical study results all make us have reason to infer, if can be with LuBO
3: Ce is prepared into high-quality monocrystalline will more have researching value, hinder this crystalline research and development but its crystal preparation is very difficult.
Summary of the invention
The purpose of this invention is to provide a kind of rear-earth-doped boric acid lutetium scandium scintillation single crystal, to overcome the deficiency of prior art.
Another object of the present invention provides a kind of float-zone method growth method of the rear-earth-doped boric acid lutetium scandium scintillation single crystal of growing.
For realizing above-mentioned purpose, technical scheme of the present invention is:
A kind of rear-earth-doped boric acid lutetium scandium scintillation single crystal is characterized in that the chemical formula of this monocrystalline is (Lu
1-xSc
x)
1-yM
yBO
3, wherein: 0.1≤x≤0.7,0＜y≤0.1, M is selected from one or more among Ce, Pr, Eu, Tb or the Yb.
Above-mentioned chemical formula (Lu
1-xSc
x)
1-yM
yBO
3In, the female and digital molar ratio relation of all representing between the corresponding chemical element of bottom right marking-up.
Preferably, 0.3≤x≤0.5,0.003＜y≤0.01.
A kind of float-zone method growth method of above-mentioned rear-earth-doped boric acid lutetium scandium scintillation single crystal may further comprise the steps:
1) batching: with Lu
2O
3, Sc
2O
3, B
2O
3And the oxide compound of element M is raw material, said raw material made compound according to crystal proportion of composing batching back thorough mixing, wherein B
2O
3Excessive 5-7wt%;
2) sintering: the compound that obtains in the step 1) with waiting static pressure to be pressed into charge bar, is carried out sintering in 900～1300 ℃ then, and sintering time is 5～100 hours, makes polycrystalline rod;
3) crystal growth: polycrystalline rod and seed crystal are installed in the stove of floating region, and sealing also feeds shielding gas, is warming up to polycrystalline rod and seed crystal then and melts; Intensification while polycrystalline rod and seed crystal are distinguished in the same way or backward rotation; Rotating speed is 10～30rpm, is incubated 10～15 minutes, inoculation; Then through necking down, shouldering, isodiametric growth and ending are carried out crystal growth, and in process of growth, the speed of growth is 3～20mm/h, and floating region length is 0.5～2 times of charge bar diameter;
4) cooling: after crystal growth finishes, drop to room temperature, obtain rear-earth-doped boric acid lutetium scandium scintillation single crystal with 100-400 ℃/hour speed.
The oxide compound of said element M is CeO
2, Pr
6O
11, Eu
2O
3, Tb
2O
3Or Yb
2O
3In one or more.
Preferable, the raw material in the said step 1) also need carry out pre-burning before batching, can carry out pre-burning under the air atmosphere with raw material at 150 ℃, and the purpose of pre-burning is in order to remove the H in the raw material
2O and CO
2
Preferable, the raw material B in the said step 1)
2O
3Excessive 5-7wt% is with by chemical formula (Lu
1-xSc
x)
1-yM
yBO
3In stoichiometric ratio calculate required B
2O
3Weight be benchmark, purpose is to guarantee B
2O
3Excessive, other oxide raw materials are all accurately by stoichiometric ratio batching.
Said step 2) concrete steps are: seal in the rubber tubing with the Φ 5～10mm that packs into behind the compound thorough mixing, static pressure such as usefulness depress to fine and close charge bar at the pressure of 100Mpa, with the Pt silk it are hung in then and carry out presintering in the retort furnace.
Preferable, said step 2) in, the pressure that waits static pressure is 100～200Mpa.
Preferably, said step 2) in, sintering temperature is 1000～1200 ℃.
Preferable, in the said step 3), shielding gas is high pure nitrogen or argon gas.
Preferably, in the said step 3), rotating speed is 15～20rpm, and the speed of growth is 6～9mm/h.
Preferably, in the said step 3), floating region length is 1～1.5 times of charge bar diameter, to keep bigger condensate depression.
Preferably, in the said step 4), cooling rate is 300 ℃/hour.
The present invention is after the relative merits that compared various growing methods; Find that float-zone method produces bigger condensate depression easily in process of growth; And because it adopts is type of heating such as halogen lamp or electron beam; Also can obtain rate of temperature fall faster easily, be a kind of growing method efficiently.Float-zone method has clear superiority for no crucible growth at aspects such as avoiding pollution.So the float-zone method growth method that the present invention adopts has high-level efficiency, low cost, advantages such as less energy-consumption.
Description of drawings
Fig. 1 (Lu
0.5Sc
0.5)
0.997Ce
0.003BO
3The X ray diffracting spectrum of monocrystalline.Can find that from collection of illustrative plates this crystalline material is a boric acid lutetium scandium sosoloid phase.
Fig. 2 (Lu
0.5Sc
0.5)
0.995Ce
0.005BO
3The excitation of X-rays emission spectrum (room temperature) of scintillation single crystal.It is luminous from collection of illustrative plates, can to observe typical cerium ion.
Fig. 3 (Lu
0.8Sc
0.2)
0.989Pr
0.01Ce
0.001BO
3The excitation of X-rays emission spectrum (room temperature) of scintillation single crystal.It is luminous luminous with cerium ion from collection of illustrative plates, can to observe typical praseodymium ion.
Fig. 4 (Lu
0.7Sc
0.3)
0.99Eu
0.01BO
3The excitation of X-rays emission spectrum (room temperature) of scintillation single crystal.It is luminous from collection of illustrative plates, can to observe typical europium ion.
Fig. 5 (Lu
0.7Sc
0.3)
0.99Tb
0.01BO
3The excitation of X-rays emission spectrum (room temperature) of scintillation single crystal.It is luminous from collection of illustrative plates, can to observe typical terbium ion.
Embodiment
Embodiment 1 (Lu
0.5Sc
0.5)
0.995Ce
0.005BO
3The growth of monocrystalline:
(1) presses under the air atmosphere before the batching at 150 ℃ of pre-burning raw materials, remove the H in the raw material
2O and CO
2, then by (Lu
0.5Sc
0.5)
0.995Ce
0.005BO
3Stoichiometric ratio is carried out proportioning, wherein B
2O
3Excessive 5wt%.At first take by weighing Lu
2O
3168.28g, Sc
2O
358.32g, B
2O
363.32g, CeO
2(1.463g material purity is 4N).
(2) seal in the rubber tubing with the Φ 10mm that packs into behind the raw material thorough mixing, static pressure such as usefulness depress to fine and close charge bar at the pressure of 100Mpa, with the Pt silk it are hung in then and carry out presintering in the retort furnace.1000 ℃ of sintering temperatures, sintering time is 20 hours, makes polycrystalline rod.
(3) polycrystalline rod is hung over the floating region furnace upper end with nichrome wire, seed crystal is contained in the lower end, installs the back with silica tube sealing and feeding argon gas; Be warming up to charge bar and seed crystal then and melt, charge bar and seed crystal rotate respectively round about simultaneously, and rotating speed is 15rpm; Be incubated 10 minutes, inoculation.
(4) speed of growth is 6mm/h, and floating region length is 1.5 times of charge bar diameter.Through the control heating power, carry out necking down, shouldering, isodiametric growth finishes up at last, and growth ending begins cooling.
(5) in the temperature-fall period, the speed cooling by 300 ℃/hour finally obtains monocrystal material.
The monocrystalline water white transparency that obtains, maximum full-size is 5 * 5 * 2mm
3Through the XRD test, be boric acid lutetium scandium sosoloid phase (as shown in Figure 1).Through the test of X-ray excitation-emission spectrum, crystal demonstrates typical C e
3+Ionoluminescence (as shown in Figure 2).
Embodiment 2 (Lu
0.7Sc
0.3)
0.995Ce
0.005BO
3The growth of monocrystalline:
(1) presses under the air atmosphere before the batching at 150 ℃ of pre-burning raw materials, remove the H in the raw material
2O and CO
2, then by (Lu
0.7Sc
0.3)
0.995Ce
0.005BO
3Stoichiometric ratio is carried out proportioning, wherein B
2O
3Excessive 7wt%.At first take by weighing Lu
2O
3274.61g, Sc
2O
340.79g, B
2O
373.81g, CeO
2(1.705g material purity is 4N).
(2) seal in the rubber tubing with the Φ 10mm that packs into behind the raw material thorough mixing, static pressure such as usefulness depress to fine and close charge bar at the pressure of 100Mpa, with the Pt silk it are hung in then and carry out presintering in the retort furnace.1000 ℃ of sintering temperatures, sintering time is 20 hours, makes polycrystalline rod.
(3) polycrystalline rod is hung over the floating region furnace upper end with nichrome wire, seed crystal is contained in the lower end, installs the back with silica tube sealing and feeding argon gas; Be warming up to charge bar and seed crystal then and melt, charge bar and seed crystal rotate respectively round about simultaneously, and rotating speed is 15rpm; Be incubated 10 minutes, inoculation.
(4) speed of growth is 6mm/h, and floating region length is 1 times of charge bar diameter.Through the control heating power, carry out necking down, shouldering, isodiametric growth finishes up at last, and growth ending begins cooling.
(5) in the temperature-fall period, the speed cooling by 300 ℃/hour finally obtains monocrystal material.
The monocrystalline water white transparency that obtains, maximum full-size is 5 * 5 * 1mm
3Through the XRD test, be boric acid lutetium scandium sosoloid phase.
Embodiment 3 (Lu
0.7Sc
0.3)
0.99Pr
0.01BO
3The growth of monocrystalline:
(1) presses under the air atmosphere before the batching at 150 ℃ of pre-burning raw materials, remove the H in the raw material
2O and CO
2, then by (Lu
0.7Sc
0.3)
0.99Pr
0.01BO
3Stoichiometric ratio is carried out proportioning, wherein B
2O
3Excessive 7wt%.At first take by weighing Lu
2O
3217.56g, Sc
2O
332.31g, B
2O
358.77g, Pr
6O
11(2.686g material purity is 4N).
(2) seal in the rubber tubing with the Φ 10mm that packs into behind the raw material thorough mixing, static pressure such as usefulness depress to fine and close charge bar at the pressure of 100Mpa, with the Pt silk it are hung in then and carry out presintering in the retort furnace.1000 ℃ of sintering temperatures, sintering time is 20 hours, makes polycrystalline rod.
(3) polycrystalline rod is hung over the floating region furnace upper end with nichrome wire, seed crystal is contained in the lower end, installs the back with silica tube sealing and feeding argon gas; Be warming up to charge bar and seed crystal then and melt, charge bar and seed crystal rotate respectively round about simultaneously, and rotating speed is 15rpm; Be incubated 10 minutes, inoculation.
(4) speed of growth is 6mm/h, and floating region length is 1.5 times of charge bar diameter.Through the control heating power, carry out necking down, shouldering, isodiametric growth finishes up at last, and growth ending begins cooling.
(5) in the temperature-fall period, the speed cooling by 300 ℃/hour obtains monocrystal material.
The monocrystalline water white transparency that obtains, maximum full-size is 5 * 5 * 5mm
3Through the XRD test, be boric acid lutetium scandium sosoloid phase.
Embodiment 4 (Lu
0.8Sc
0.2)
0.989Pr
0.01Ce
0.001BO
3The growth of monocrystalline:
(1) presses under the air atmosphere before the batching at 150 ℃ of pre-burning raw materials, remove the H in the raw material
2O and CO
2, then by (Lu
0.8Sc
0.2)
0.989Pr
0.01Ce
0.001BO
3Stoichiometric ratio is carried out proportioning, wherein B
2O
3Excessive 7wt%.At first take by weighing Lu
2O
3227.25g, Sc
2O
319.70g, B
2O
353.80g, Pr
6O
112.459g, CeO
2(0.2486 material purity is 4N).
(2) seal in the rubber tubing with the Φ 10mm that packs into behind the raw material thorough mixing, static pressure such as usefulness depress to fine and close charge bar at the pressure of 100Mpa, with the Pt silk it are hung in then and carry out presintering in the retort furnace.1000 ℃ of sintering temperatures, sintering time is 20 hours, makes polycrystalline rod.
(3) polycrystalline rod is hung over the floating region furnace upper end with nichrome wire, seed crystal is contained in the lower end, installs the back with silica tube sealing and feeding argon gas; Be warming up to charge bar and seed crystal then and melt, charge bar and seed crystal rotate respectively round about simultaneously, and rotating speed is 15rpm; Be incubated 10 minutes, inoculation.
(4) speed of growth is 6mm/h, and floating region length is 1.5 times of charge bar diameter.Through the control heating power, carry out necking down, shouldering, isodiametric growth finishes up at last, and growth ending begins cooling.
(5) in the temperature-fall period, the speed cooling by 300 ℃/hour obtains monocrystal material.
The monocrystalline water white transparency that obtains, maximum full-size is 5 * 5 * 1mm
3Through the XRD test, be boric acid lutetium scandium sosoloid phase.Through the test of X-ray excitation-emission spectrum, crystal demonstrates typical C e
3+Ionoluminescence and Pr
3+Ionoluminescence (as shown in Figure 3).
Embodiment 5 (Lu
0.7Sc
0.3)
0.99Eu
0.01BO
3The growth of monocrystalline:
(1) presses under the air atmosphere before the batching at 150 ℃ of pre-burning raw materials, remove the H in the raw material
2O and CO
2, then by (Lu
0.7Sc
0.3)
0.99Eu
0.01BO
3Stoichiometric ratio is carried out proportioning, wherein B
2O
3Excessive 7wt%.At first take by weighing Lu
2O
3212.20g, Sc
2O
331.52g, B
2O
357.32g, Eu
2O
3(2.708g material purity is 4N).
(2) seal in the rubber tubing with the Φ 10mm that packs into behind the raw material thorough mixing, static pressure such as usefulness depress to fine and close charge bar at the pressure of 100Mpa, with the Pt silk it are hung in then and carry out presintering in the retort furnace.1000 ℃ of sintering temperatures, sintering time is 20 hours, makes polycrystalline rod.
(3) polycrystalline rod is hung over the floating region furnace upper end with nichrome wire, seed crystal is contained in the lower end, installs the back with silica tube sealing and feeding argon gas; Be warming up to charge bar and seed crystal then and melt, charge bar and seed crystal rotate respectively round about simultaneously, and rotating speed is 15rpm; Be incubated 10 minutes, inoculation.
(4) speed of growth is 9mm/h, and floating region length is 1 times of charge bar diameter.Through the control heating power, carry out necking down, shouldering, isodiametric growth finishes up at last, and growth ending begins cooling.
(5) in the temperature-fall period, the speed cooling by 300 ℃/hour finally obtains monocrystal material.
The monocrystalline water white transparency that obtains, maximum full-size is 5 * 5 * 1mm
3Through the XRD test, be boric acid lutetium scandium sosoloid phase.Through the test of X-ray excitation-emission spectrum, crystal demonstrates typical Eu
3+Ionoluminescence (as shown in Figure 4).
Embodiment 6 (Lu
0.7Sc
0.3)
0.995Eu
0.005BO
3The growth of monocrystalline:
(1) presses under the air atmosphere before the batching at 150 ℃ of pre-burning raw materials, remove the H in the raw material
2O and CO
2, then by (Lu
0.7Sc
0.3)
0.995Eu
0.005BO
3Stoichiometric ratio is carried out proportioning, wherein B
2O
3Excessive 7wt%.At first take by weighing Lu
2O
3213.41g, Sc
2O
331.70g, B
2O
357.36g, Eu
2O
3(1.355g material purity is 4N).
(2) seal in the rubber tubing with the Φ 10mm that packs into behind the raw material thorough mixing, static pressure such as usefulness depress to fine and close charge bar at the pressure of 100Mpa, with the Pt silk it are hung in then and carry out presintering in the retort furnace.1000 ℃ of sintering temperatures, sintering time is 18 hours, makes polycrystalline rod.
(3) polycrystalline rod is hung over the floating region furnace upper end with nichrome wire, seed crystal is contained in the lower end, installs the back with silica tube sealing and feeding argon gas; Be warming up to charge bar and seed crystal then and melt, charge bar and seed crystal rotate respectively round about simultaneously, and rotating speed is 15rpm; Be incubated 10 minutes, inoculation.
(4) speed of growth is 9mm/h, and floating region length is 1 times of charge bar diameter.Through the control heating power, carry out necking down, shouldering, isodiametric growth finishes up at last, and growth ending begins cooling.
(5) in the temperature-fall period, the speed cooling by 300 ℃/hour finally obtains monocrystal material.
The monocrystalline water white transparency that obtains, maximum full-size is 5 * 5 * 1mm
3Through the XRD test, be boric acid lutetium scandium sosoloid phase.Through the test of X-ray excitation-emission spectrum, crystal demonstrates typical Eu
3+Ionoluminescence.
Embodiment 7 (Lu
0.3Sc
0.7)
0.997Eu
0.003BO
3The growth of monocrystalline:
(1) presses under the air atmosphere before the batching at 150 ℃ of pre-burning raw materials, remove the H in the raw material
2O and CO
2, then by (Lu
0.3Sc
0.7)
0.997Eu
0.003BO
3Stoichiometric ratio is carried out proportioning, wherein B
2O
3Excessive 7wt%.At first take by weighing Lu
2O
3124.97g, Sc
2O
3101.06g, B
2O
378.22g, Eu
2O
3(1.109g material purity is 4N).
(2) seal in the rubber tubing with the Φ 10mm that packs into behind the raw material thorough mixing, static pressure such as usefulness depress to fine and close charge bar at the pressure of 100Mpa, with the Pt silk it are hung in then and carry out presintering in the retort furnace.1000 ℃ of sintering temperatures, sintering time is 20 hours, makes polycrystalline rod.
(3) polycrystalline rod is hung over the floating region furnace upper end with nichrome wire, seed crystal is contained in the lower end, installs the back with silica tube sealing and feeding argon gas; Be warming up to charge bar and seed crystal then and melt, charge bar and seed crystal rotate respectively round about simultaneously, and rotating speed is 15rpm; Be incubated 10 minutes, inoculation.
(4) speed of growth is 9mm/h, and floating region length is 1 times of charge bar diameter.Through the control heating power, carry out necking down, shouldering, isodiametric growth finishes up at last, and growth ending begins cooling.
(5) in the temperature-fall period, the speed cooling by 300 ℃/hour finally obtains monocrystal material.
The monocrystalline water white transparency that obtains, maximum full-size is 5 * 5 * 1mm
3Through the XRD test, be boric acid lutetium scandium sosoloid phase.Through the test of X-ray excitation-emission spectrum, crystal demonstrates typical Eu
3+Ionoluminescence.
Embodiment 8 (Lu
0.7Sc
0.3)
0.99Tb
0.01BO
3The growth of monocrystalline:
(1) presses under the air atmosphere before the batching at 150 ℃ of pre-burning raw materials, remove the H in the raw material
2O and CO
2, then by (Lu
0.7Sc
0.3)
0.99Tb
0.01BO
3Stoichiometric ratio is carried out proportioning, wherein B
2O
3Excessive 7wt%.At first take by weighing Lu
2O
3212.12g, Sc
2O
331.51g, B
2O
361.31g, Tb
4O
7(2.875g material purity is 4N).
(2) seal in the rubber tubing with the Φ 10mm that packs into behind the raw material thorough mixing, static pressure such as usefulness depress to fine and close charge bar at the pressure of 100Mpa, with the Pt silk it are hung in then and carry out presintering in the retort furnace.1200 ℃ of sintering temperatures, sintering time is 20 hours, makes polycrystalline rod.
(3) polycrystalline rod is hung over the floating region furnace upper end with nichrome wire, seed crystal is contained in the lower end, installs the back with silica tube sealing and feeding argon gas; Be warming up to charge bar and seed crystal then and melt, charge bar and seed crystal rotate respectively round about simultaneously, and rotating speed is 20rpm; Be incubated 15 minutes, inoculation.
(4) speed of growth is 9mm/h, and floating region length is 1 times of charge bar diameter.Through the control heating power, carry out necking down, shouldering, isodiametric growth finishes up at last, and growth ending begins cooling.
(5) in the temperature-fall period, the speed cooling by 300 ℃/hour finally obtains monocrystal material.The monocrystalline water white transparency that obtains, maximum full-size is 5 * 5 * 1mm
3Through the XRD test, be boric acid lutetium scandium sosoloid phase.Through the test of X-ray excitation-emission spectrum, crystal demonstrates typical Tb
3+Ionoluminescence (as shown in Figure 5).
Embodiment 9 (Lu
0.5Sc
0.5)
0.997Tb
0.003BO
3The growth of monocrystalline:
(1) presses under the air atmosphere before the batching at 150 ℃ of pre-burning raw materials, remove the H in the raw material
2O and CO
2, then by (Lu
0.5Sc
0.5)
0.997Tb
0.003BO
3Stoichiometric ratio is carried out proportioning, wherein B
2O
3Excessive 7wt%.At first take by weighing Lu
2O
3176.15g, Sc
2O
361.05g, B
2O
366.15g, Tb
4O
7(0.996g material purity is 4N).
(2) seal in the rubber tubing with the Φ 10mm that packs into behind the raw material thorough mixing, static pressure such as usefulness depress to fine and close charge bar at the pressure of 100Mpa, with the Pt silk it are hung in then and carry out presintering in the retort furnace.1200 ℃ of sintering temperatures, sintering time is 20 hours, makes polycrystalline rod.
(3) polycrystalline rod is hung over the floating region furnace upper end with nichrome wire, seed crystal is contained in the lower end, installs the back with silica tube sealing and feeding argon gas; Be warming up to charge bar and seed crystal then and melt, charge bar and seed crystal rotate respectively round about simultaneously, and rotating speed is 20rpm; Be incubated 15 minutes, inoculation.
(4) speed of growth is 9mm/h, and floating region length is 1 times of charge bar diameter.Through the control heating power, carry out necking down, shouldering, isodiametric growth finishes up at last, and growth ending begins cooling.
(5) in the temperature-fall period, the speed cooling by 300 ℃/hour finally obtains monocrystal material.The monocrystalline water white transparency that obtains, maximum full-size is 5 * 5 * 1mm
3Through the XRD test, be boric acid lutetium scandium sosoloid phase.Through the test of X-ray excitation-emission spectrum, crystal demonstrates typical Tb
3+Ionoluminescence
Embodiment 10 (Lu
0.8Sc
0.2)
0.993Tb
0.007BO
3The growth of monocrystalline:
(1) presses under the air atmosphere before the batching at 150 ℃ of pre-burning raw materials, remove the H in the raw material
2O and CO
2, then by (Lu
0.8Sc
0.2)
0.993Tb
0.007BO
3Stoichiometric ratio is carried out proportioning, wherein B
2O
3Excessive 7wt%.At first take by weighing Lu
2O
3228.14g, Sc
2O
319.77g, B
2O
353.76g, Tb
4O
7(1.889g material purity is 4N).
(2) seal in the rubber tubing with the Φ 10mm that packs into behind the raw material thorough mixing, static pressure such as usefulness depress to fine and close charge bar at the pressure of 100Mpa, with the Pt silk it are hung in then and carry out presintering in the retort furnace.1200 ℃ of sintering temperatures, sintering time is 20 hours, makes polycrystalline rod.
(3) polycrystalline rod is hung over the floating region furnace upper end with nichrome wire, seed crystal is contained in the lower end, installs the back with silica tube sealing and feeding argon gas; Be warming up to charge bar and seed crystal then and melt, charge bar and seed crystal rotate respectively round about simultaneously, and rotating speed is 20rpm; Be incubated 15 minutes, inoculation.
(4) speed of growth is 9mm/h, and floating region length is 1 times of charge bar diameter.Through the control heating power, carry out necking down, shouldering, isodiametric growth finishes up at last, and growth ending begins cooling.
(5) in the temperature-fall period, the speed cooling by 300 ℃/hour finally obtains monocrystal material.The monocrystalline water white transparency that obtains, maximum full-size is 5 * 5 * 1mm
3Through the XRD test, be boric acid lutetium scandium sosoloid phase.Through the test of X-ray excitation-emission spectrum, crystal demonstrates typical Tb
3+Ionoluminescence.
Embodiment 11 (Lu
0.7Sc
0.3)
0.99Yb
0.01BO
3The growth of monocrystalline:
(1) presses under the air atmosphere before the batching at 150 ℃ of pre-burning raw materials, remove the H in the raw material
2O and CO
2, then by (Lu
0.7Sc
0.3)
0.99Yb
0.01BO
3Stoichiometric ratio is carried out proportioning, wherein B
2O
3Excessive 7wt%.At first take by weighing Lu
2O
3217.20g, Sc
2O
332.26g, B
2O
358.67g, Yb
2O
3(3.104g material purity is 4N).
(2) seal in the rubber tubing with the Φ 10mm that packs into behind the raw material thorough mixing, static pressure such as usefulness depress to fine and close charge bar at the pressure of 100Mpa, with the Pt silk it are hung in then and carry out presintering in the retort furnace.1200 ℃ of sintering temperatures, sintering time is 20 hours, makes polycrystalline rod.
(3) polycrystalline rod is hung over the floating region furnace upper end with nichrome wire, seed crystal is contained in the lower end, installs the back with silica tube sealing and feeding argon gas; Be warming up to charge bar and seed crystal then and melt, charge bar and seed crystal rotate respectively round about simultaneously, and rotating speed is 15rpm; Be incubated 10 minutes, inoculation.
(4) speed of growth is 9mm/h, and floating region length is 1 times of charge bar diameter.Through the control heating power, carry out necking down, shouldering, isodiametric growth finishes up at last, and growth ending begins cooling.
(5) in the temperature-fall period, the speed cooling by 300 ℃/hour finally obtains monocrystal material.
The monocrystalline water white transparency that obtains, maximum full-size is 5 * 5 * 1mm
3Through the XRD test, be boric acid lutetium scandium sosoloid phase.
Claims (7)
1. the float-zone method growth method of a rear-earth-doped boric acid lutetium scandium scintillation single crystal, the chemical formula of said monocrystalline is (Lu
1-xSc
x)
1-yM
yBO
3, wherein: 0.1≤x≤0.7,0＜y≤0.1, M is selected from one or more among Ce, Pr, Eu, Tb or the Yb, may further comprise the steps:
1) batching: with Lu
2O
3, Sc
2O
3, B
2O
3And the oxide compound of element M is raw material, said raw material made compound according to crystal proportion of composing batching back thorough mixing, wherein B
2O
3Excessive 5-7wt%;
2) sintering: the compound that obtains in the step 1) with waiting static pressure to be pressed into charge bar, is carried out sintering in 900～1300 ℃ then, and sintering time is 5～100 hours, makes polycrystalline rod;
3) crystal growth: polycrystalline rod and seed crystal are installed in the stove of floating region, and sealing also feeds shielding gas, is warming up to polycrystalline rod and seed crystal then and melts; Intensification while polycrystalline rod and seed crystal are distinguished in the same way or backward rotation; Rotating speed is 10～30rpm, is incubated 10～15 minutes, inoculation; Then through necking down, shouldering, isodiametric growth and ending are carried out crystal growth, and in process of growth, the speed of growth is 3～20mm/h, and floating region length is 0.5～2 times of charge bar diameter;
4) cooling: after crystal growth finishes, drop to room temperature, obtain rear-earth-doped boric acid lutetium scandium scintillation single crystal with 100-400 ℃/hour speed.
2. the float-zone method growth method of rear-earth-doped boric acid lutetium scandium scintillation single crystal as claimed in claim 1 is characterized in that the oxide compound of said element M is CeO
2, Pr
6O
11, Eu
2O
3, Tb
2O
3Or Yb
2O
3In one or more.
3. the float-zone method growth method of rear-earth-doped boric acid lutetium scandium scintillation single crystal as claimed in claim 1 is characterized in that said step 2) in, the pressure that waits static pressure is 100～200Mpa.
4. the float-zone method growth method of rear-earth-doped boric acid lutetium scandium scintillation single crystal as claimed in claim 1 is characterized in that said step 2) in, sintering temperature is 1000～1200 ℃.
5. the float-zone method growth method of rear-earth-doped boric acid lutetium scandium scintillation single crystal as claimed in claim 1 is characterized in that, in the said step 3), rotating speed is 15～20rpm, and the speed of growth is 6～9mm/h.
6. the float-zone method growth method of rear-earth-doped boric acid lutetium scandium scintillation single crystal as claimed in claim 1 is characterized in that, in the said step 3), floating region length is 1～1.5 times of charge bar diameter.
7. like the float-zone method growth method of arbitrary described rear-earth-doped boric acid lutetium scandium scintillation single crystal among the claim 1-6, it is characterized in that 0.3≤x≤0.5,0.003＜y≤0.01.
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|---|---|---|---|---|
| CN101545137A (en) * | 2008-03-25 | 2009-09-30 | 中国科学院福建物质结构研究所 | Erbium ion activated borate laser crystal and method for preparing same and application thereof |
| CN101871125A (en) * | 2010-06-03 | 2010-10-27 | 山东大学 | High-temperature rare earth oxide laser crystal and preparation method thereof |
| CN101955773A (en) * | 2010-10-09 | 2011-01-26 | 中国科学院上海硅酸盐研究所 | Praseodymium and cerium-doped lutetium scandium borate luminous material and preparation method thereof |
| CN102061167A (en) * | 2010-09-03 | 2011-05-18 | 中国科学院上海硅酸盐研究所 | Preparation method and application of rare earth-doped calcite phase lutetium borate crystal |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101545137A (en) * | 2008-03-25 | 2009-09-30 | 中国科学院福建物质结构研究所 | Erbium ion activated borate laser crystal and method for preparing same and application thereof |
| CN101871125A (en) * | 2010-06-03 | 2010-10-27 | 山东大学 | High-temperature rare earth oxide laser crystal and preparation method thereof |
| CN102061167A (en) * | 2010-09-03 | 2011-05-18 | 中国科学院上海硅酸盐研究所 | Preparation method and application of rare earth-doped calcite phase lutetium borate crystal |
| CN101955773A (en) * | 2010-10-09 | 2011-01-26 | 中国科学院上海硅酸盐研究所 | Praseodymium and cerium-doped lutetium scandium borate luminous material and preparation method thereof |
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| Shun-Ichi Hatamoto et al.Growth and scintillation properties of cerium doped lutetium scandium borate single crystals.《Journal of Crystal Growth》.2009,第530页右栏第1段到第533页右栏第1段. * |
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