CN1322173C - Preparation method of cerium-doped lutetium disilicate high-temperature scintillation single crystal - Google Patents
Preparation method of cerium-doped lutetium disilicate high-temperature scintillation single crystal Download PDFInfo
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- CN1322173C CN1322173C CNB2004100534382A CN200410053438A CN1322173C CN 1322173 C CN1322173 C CN 1322173C CN B2004100534382 A CNB2004100534382 A CN B2004100534382A CN 200410053438 A CN200410053438 A CN 200410053438A CN 1322173 C CN1322173 C CN 1322173C
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- 239000013078 crystal Substances 0.000 title claims abstract description 104
- 238000002360 preparation method Methods 0.000 title claims description 14
- NAEKEHKTSNMBKE-UHFFFAOYSA-N [Si]([O-])([O-])([O-])O[Si]([O-])([O-])[O-].[Lu+3].[Lu+3] Chemical compound [Si]([O-])([O-])([O-])O[Si]([O-])([O-])[O-].[Lu+3].[Lu+3] NAEKEHKTSNMBKE-UHFFFAOYSA-N 0.000 title 1
- 239000002994 raw material Substances 0.000 claims abstract description 34
- 238000000034 method Methods 0.000 claims abstract description 31
- 229910052765 Lutetium Inorganic materials 0.000 claims abstract description 27
- 239000000463 material Substances 0.000 claims abstract description 25
- OHSVLFRHMCKCQY-UHFFFAOYSA-N lutetium atom Chemical compound [Lu] OHSVLFRHMCKCQY-UHFFFAOYSA-N 0.000 claims abstract description 24
- 229910052684 Cerium Inorganic materials 0.000 claims abstract description 20
- 230000008569 process Effects 0.000 claims abstract description 16
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 claims abstract description 14
- 238000002844 melting Methods 0.000 claims abstract description 14
- 230000008018 melting Effects 0.000 claims abstract description 14
- 229910052726 zirconium Inorganic materials 0.000 claims abstract description 7
- KDJOAYSYCXTQGG-UHFFFAOYSA-N disilicic acid Chemical compound O[Si](O)(O)O[Si](O)(O)O KDJOAYSYCXTQGG-UHFFFAOYSA-N 0.000 claims description 18
- 238000005303 weighing Methods 0.000 claims description 12
- 238000005516 engineering process Methods 0.000 claims description 10
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 9
- 238000002156 mixing Methods 0.000 claims description 7
- 239000000126 substance Substances 0.000 claims description 7
- 238000001816 cooling Methods 0.000 claims description 6
- 238000010438 heat treatment Methods 0.000 claims description 6
- 229910052761 rare earth metal Inorganic materials 0.000 claims description 6
- 238000009331 sowing Methods 0.000 claims description 6
- 238000010792 warming Methods 0.000 claims description 6
- LHXYFSDEWOLMCQ-UHFFFAOYSA-N cerium lutetium trihydroxy(trihydroxysilyloxy)silane Chemical compound [Lu].[Si](O)(O)(O)O[Si](O)(O)O.[Ce] LHXYFSDEWOLMCQ-UHFFFAOYSA-N 0.000 claims description 5
- 229910021645 metal ion Inorganic materials 0.000 claims description 5
- 239000000843 powder Substances 0.000 claims description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 4
- 238000002425 crystallisation Methods 0.000 claims description 4
- 230000008025 crystallization Effects 0.000 claims description 4
- 239000010439 graphite Substances 0.000 claims description 4
- 230000006698 induction Effects 0.000 claims description 4
- 238000007789 sealing Methods 0.000 claims description 4
- 229910052741 iridium Inorganic materials 0.000 claims description 3
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 claims description 3
- 238000009766 low-temperature sintering Methods 0.000 claims description 3
- 239000011812 mixed powder Substances 0.000 claims description 3
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims description 3
- 229910052721 tungsten Inorganic materials 0.000 claims description 3
- 239000010937 tungsten Substances 0.000 claims description 3
- 241000209456 Plumbago Species 0.000 claims 2
- 238000006243 chemical reaction Methods 0.000 abstract description 5
- 230000001603 reducing effect Effects 0.000 abstract description 4
- 150000001875 compounds Chemical class 0.000 abstract description 3
- 229910052715 tantalum Inorganic materials 0.000 abstract description 2
- 229910052581 Si3N4 Inorganic materials 0.000 abstract 1
- 229910000421 cerium(III) oxide Inorganic materials 0.000 abstract 1
- 229910052681 coesite Inorganic materials 0.000 abstract 1
- 229910052906 cristobalite Inorganic materials 0.000 abstract 1
- 230000005855 radiation Effects 0.000 abstract 1
- 229910001404 rare earth metal oxide Inorganic materials 0.000 abstract 1
- 239000000377 silicon dioxide Substances 0.000 abstract 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 abstract 1
- 229910052682 stishovite Inorganic materials 0.000 abstract 1
- 238000003786 synthesis reaction Methods 0.000 abstract 1
- 229910052905 tridymite Inorganic materials 0.000 abstract 1
- 150000002500 ions Chemical class 0.000 description 10
- -1 cerium ion Chemical class 0.000 description 7
- 239000000203 mixture Substances 0.000 description 5
- 238000009206 nuclear medicine Methods 0.000 description 5
- 230000005658 nuclear physics Effects 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- 229910052688 Gadolinium Inorganic materials 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 229910052727 yttrium Inorganic materials 0.000 description 3
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 2
- 229910052737 gold Inorganic materials 0.000 description 2
- 239000010931 gold Substances 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 230000003287 optical effect Effects 0.000 description 2
- 238000005245 sintering Methods 0.000 description 2
- 241000024287 Areas Species 0.000 description 1
- 240000003936 Plumbago auriculata Species 0.000 description 1
- 230000003471 anti-radiation Effects 0.000 description 1
- 229910001632 barium fluoride Inorganic materials 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 238000007689 inspection Methods 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 238000004020 luminiscence type Methods 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
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- 230000009467 reduction Effects 0.000 description 1
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- Crystals, And After-Treatments Of Crystals (AREA)
- Luminescent Compositions (AREA)
Abstract
Cerium-doped lutetium pyrosilicate high-temperature scintillation crystal Lu2(1-x-y-z)Re2xCe2yM2zSi2O7The key point of the method is that CeO is introduced in the process of preparing raw materials2Equi-equivalent of strongly reducing Si3N4Raw materials, trace Zr, Ta or Mg and other elements are introduced, and CeO is added in the processes of temperature rise material melting and crystal growth2Reduction to Ce2O3Then with SiO2And Re2O3Synthesis of cerium-containing compounds by reaction of oxides3+Ionic lutetium pyrosilicate high-temperature scintillation single crystals. Ce is contained in the cerium-doped lutetium pyrosilicate high-temperature scintillation crystal prepared by the method4+The ion is minimum, and the crystal lattice integrity and the radiation resistance are better.
Description
Technical field:
The present invention relates to field of crystal growth, particularly doping trivalent cerium ion (Ce
3+) disilicic acid lutetium high temperature scintillating monocrystal: Lu
2 (1-x-y-z)Re
2xCe
2yM
2zSi
2O
7(wherein Re represents other rare earth element except that Lu, as: one of Y, Gd, Sc, Yb etc. or multiple mixing, M represents metal ions such as Zr, Mg, Ta; 0≤x≤0.3,0.001≤y≤.05,0.00001≤z≤0.0005), and growth method.Be specifically related at initial oxidation raw material (Lu
2O
3, Re
2O
3, CeO
2, SiO
2) the middle adding and CeO
2Si Deng molar equivalent
3N
4Raw material adopts crystal pulling method, falling crucible method and other melt growth method to be prepared and mixes trivalent cerium ion disilicic acid lutetium high temperature scintillation crystal.
Background technology:
Inorganic scintillation crystal can be widely used in research Application Areass such as high energy physics nuclear physics detecting, image nuclear medicine (PET, CT), industrial online detection, safety inspection, geology archaeology, celestial observation.The BGO scintillation crystal is traditional inorganic scintillation crystal, and its biggest advantage is to have bigger density and effective atomic number (ρ=7.13g/em
3, Z
Eff=74), therefore has broad application background in high energy physics nuclear physics and nuclear medicine diagnostic fields such as (PET).But there is light output little (light output is about 7-10%Nal (Tl) relatively) in the BGO crystal, grows shortcomings such as (300ns) fall time, and this has just limited BGO crystalline range of application greatly.
The high-temperature oxide scintillation crystal of Ce ion doping as: Ce:GSO, Ce:LSO, Ce:YAP, Ce:LuAP etc. are the novel scintillator crystal materials of a class that comes across the end of the eighties in last century-nineties.With traditional NaI:T1, BGO, BaF2, low melting points such as PWO (being no more than 1500 ℃) inorganic scintillation crystal is compared, the high-temperature oxide scintillation crystal of Ce ion doping is exported (being about BGO crystalline 2-10 doubly) and fast decay (being about BGO crystalline 1/5-1/20) with high light, and therefore, this scintillation crystals enjoys people's attention, referring to: 2002 " artificial lens journal " the 31st the 3rd phase of volume, 291-297 page or leaf.Wherein, the Ce:LSO scintillation crystal is the scintillation crystal that paid close attention to by people at present, compare with the BGO crystal, the Ce:LSO scintillation crystal has higher light output (being about 7 times of BGO crystalline), optical attenuation constant (being about BGO crystalline 1/7) reaches density and the effective atomic number (ρ=7.4g/cm suitable with the BGO crystal faster
3, Z
Eff=66), referring to U.S.Pat.No:4,958,080.But the Ce:LSO scintillation crystal has and contains a large amount of Lu elements in high melt point (being about 2200 ℃), the crystal and have shortcomings such as natural radioactivity, so this scintillation crystal is difficult to preparation and the detector made has higher background noise.
Recently, people have found cerium ion-doped disilicic acid lutetium crystal (Ce:Lu again
2-xM
xSi
2O
7, be called for short Ce:LPS) and be a kind of inorganic scintillation crystal preferably, this crystal belongs to oblique system, and lattice parameter is respectively: a=6.765 , b=8.839 , c=4.715 , β=101.96 °, density and effective atomic number are respectively 6.23g/cm
3And Z
Eff=64.The Ce:LPS scintillation crystal has higher light output and is about 13000-22000Ph/MeV, optical attenuation (being about 30ns) faster, more attractive attention be that this crystalline fusing point has only 1900 ℃, reduced about 200-300 ℃ than the LSO crystal, therefore more or less freely preparation, referring to: U.S.Pat.No:6,437,336.
Cerium ion-doped high temperature scintillation crystal belongs to extrinsic scintillation crystal, and trivalent cerium ion is the luminescence center in the crystal.Its luminescence mechanism is commonly considered as being finished by following 3 steps, and (a) at first scintillation crystal absorbs energetic ray or particle, thereby produces a large amount of electron-hole pairs in lattice; (b) a large amount of high-octane electron-hole pairs carry out relaxation by the interaction between electronics one electronics, electronics one phonon, and it is right to become the thermalized electron hole with energy gap energy at last, and the thermalized electron hole is to transferring energy to Ce again
3+The ionoluminescence center; (c) Ce
3+Ion is sent out twinkling light by the transition of 5d-4f.Studies show that, contain Ce in the crystal
4+During ion, will quencher Ce
3+Thereby the ionoluminescence center reduces the light output of scintillation crystal.Referring to: Journal ofLuminescience 87-89 phase,, 266-268 page or leaf in 2000; Journal of Luminescience 60-611994 P963-966; Nuclear Instruments and Methods in Physics Research A the 320th volume 1992, the 263-272 page or leaf.
Formerly in the technology, cerium ion-doped rare earth disilicic acid lutetium series scintillation crystal (Ce:Lu
2-xM
xSi
2O
7, be called for short Ce:LPS), in crystal growing process, the general Ce:Lu that directly adopts
2-xM
xSi
2O
7Oxide compound (the Re of correspondence in the chemical formula
2O
3, SiO
2And Ce
2O
3) raw material prepares in molar ratio that the synthetic polycrystal grows, referring to U.S.Pat.No:6,437,336.
Formerly the cerium ion-doped Ce:LPS scintillation crystal of technology growth has following shortcoming: because Ce
2O
3Raw material is easy to become stable tetravalence attitude ion when carrying out sintering in air atmosphere or weak oxide atmosphere, and adopt melt growth methods such as crystal pulling method, float-zone method to be weak oxide atmosphere, the crystal of Huo Deing will contain a certain amount of quadrivalent cerium ion at last, thereby has reduced the output of crystalline light.
In addition, formerly there is more lattice imperfection in the Ce:LPS scintillation crystal of technology growth, thereby reduced the crystalline scintillation properties.
Summary of the invention:
The objective of the invention is to overcome the shortcoming of technology formerly, provide a kind of preparation method who mixes cerium disilicic acid lutetium high temperature scintillation crystal, this single crystal Lu
2 (1-x-y-z)Re
2xCe
2yM
2zSi
2O
7Contain Ce
4+Ion is minimum, has perfection of lattice and anti-radiation performance preferably.
Technical solution of the present invention is as follows:
Key of the present invention is in the process of preparation raw material, introduces and CeO
2The Si of equivalent strong reducing property
3N
4Raw material, and introduce elements such as Zr, the Ta of trace or Mg, and in temperature increasing for melting materials and crystal growing process with CeO
2Be reduced into Ce
2O
3, again with SiO
2And Re
2O
3Deng the synthetic Ce that contains of oxide compound reaction
3+Ionic disilicic acid lutetium high temperature scintillating monocrystal.
Technical solution of the present invention is as follows:
A kind of preparation method who mixes cerium disilicic acid lutetium high temperature scintillating monocrystal, this method comprises the following steps::
1. press the chemical formula Lu of doping trivalent cerium ion disilicic acid lutetium
2 (1-x-y-z)Re
2xCe
2yM
2zSi
2O
7Prepare burden, wherein Re represents other rare earth element except that Lu, and M represents Zr, Mg, Ta metal ion; 0≤x≤0.3,0.001≤y≤0.05,0.00001≤z≤0.0005 is behind selected x, y, the z, by the mol ratio of each component oxide correspondence, i.e. Lu
2O
3: Re
2O
3: CeO
2: MO
2: SiO
2=(1-x-y-z): x: 2y: 2z: 2 weighing initial feed, the purity of each initial feed are all greater than 99.99%, and then take by weighing and CeO
2The Si of equivalent mole
3N
4Raw material, the i.e. Si of y/6 mole
3N
4Raw material;
2. each component raw material thorough mixing is become uniform mixed powder;
3. under the pressure of 1-5Gpa, the blended powder is pressed into columned material cake, carried out low-temperature sintering 10-24 hour being lower than under 500 ℃ the temperature;
4. with in the packaged Iridium Crucible of advancing in the burner hearth of burned material, with the burner hearth sealing and vacuumize, vacuum tightness is about 10
-3-10
-4Pa is in order to guarantee CeO
2Fully reduced, under this vacuum tightness, adopt the Frequency Induction Heating mode to carry out temperature increasing for melting materials with 300-500 ℃/hr heat-up rate;
5. locate when the interior material piece of crucible is warmed up to 1000-1200 ℃, carried out constant temperature 2-3 hour in this temperature range;
6. continue to be warming up to 1900-2000 ℃ with the heat-up rate of 300-500 ℃ of ./hr, wait to expect all fusings after, in this temperature range constant temperature 1-2 hour again;
7. in burner hearth, slowly charge into N
2Gas or Ar gas make the air pressure of burner hearth remain on 1-1.25atm, then, under the Tc of single crystal of the present invention, generally in 1850-1950 ℃ of scope, adopt the cerium ion-doped disilicic acid lutetium high temperature scintillation crystal of technology growth of crystal pulling method, in crystal growing process, adopt pure Lu
2Si
2O
7Seed crystal, the speed of growth are 1-5mm/hr, and the crystal rotating speed is 10-80RPM, crystal through sowing, behind undergauge, shouldering, isometrical, ending and the cooling process, crystal growth is finished.
Described temperature increasing for melting materials adopts plumbago crucible, perhaps tungsten crucible.
Described Lu
2Si
2O
7The seed crystal direction is axial or other crystallization direction of a, b, c.
The present invention compares with technology formerly since in initial feed by adding strong reducing property Si
3N
4Raw material, in vacuum atmosphere with stable CeO
2The raw material reduction is incorporated in the disilicic acid lutetium high temperature scintillation crystal for tervalent cerium ion.Since in disilicic acid lutetium crystal, added the Zr of trace, Mg, and elements such as Ta can suitably be corrected the distortion of lattice, have increased the anti-irradiation ability of crystalline greatly.In addition, owing in the preparation raw material process, added the Si of equivalent
3N
4Raw material, the Si element is excessive relatively, can remedy SiO in crystal growing process
2The scarce Si element problem that volatilization brings.
Embodiment:
Introducing Si of the present invention
3N
4Behind the raw material, in the temperature increasing for melting materials process, make full use of Si
3N
4Strong reducing property, impel and contain a large amount of Ce in melt and the crystal
3+Ion.Simultaneously, since trace Zr, Ta, and the adding of different valence state element such as Mg can also be eliminated the colour center that causes owing to variation of valence, thereby increase the anti-irradiation ability of crystalline greatly, has also increased the LPS perfection of lattice simultaneously.
In the temperature increasing for melting materials process in the raw material following chemical reaction will take place:
Si
3N
4+12CeO
2→6Ce
2O
3+3SiO
2+2N
2?↑ (1)
Doping trivalent cerium ion (Ce of the present invention
3+) disilicic acid lutetium high temperature scintillating monocrystal: Lu
2 (1-x-y-z)Re
2xCe
2yM
2zSi
2O
7(wherein Re represents other rare earth element except that Lu, as: one of Y, Gd, Sc, Yb etc. or multiple mixing, M represents metal ions such as Zr, Mg, Ta; 0≤x≤0.3,0.001≤y≤0.05,0.00001≤z≤0.0005) concrete fabricating technology scheme is as follows:
＜1〉by doping trivalent cerium ion disilicic acid lutetium chemical formula Lu
2 (1-x-y-z)Re
2xCe
2yM
2zSi
2O
7In the mol ratio of each component oxide correspondence carry out the weighing initial feed, the purity of each initial feed is all greater than 99.99%.Each component raw material that is promptly taken by weighing and mole proportioning thereof are as follows: Lu
2O
3: Re
2O
3: CeO
2: MO
2: SiO
2=(1-x-y-z): x: 2y: 2z: 2.And then take by weighing and CeO
2The Si of equivalent mole
3N
4Raw material, the i.e. Si of y/6 mole
3N
4Raw material adds in the above-mentioned oxide raw material.
＜2〉above-mentioned each component raw material thorough mixing that takes by weighing is become uniform mixed powder;
＜3〉will mix raw material, under the pressure of 1-5Gpa, the blended powder is pressed into columned material cake (material cake diameter is slightly less than the vessels crucible diameter), under being lower than 500 ℃ temperature, carries out low-temperature sintering 10-24 hour to remove organism, water and the low melting point impurity in the raw material;
＜4〉with in the packaged Ir gold crucible that advances in the burner hearth of burned material, with the burner hearth sealing and vacuumize, vacuum tightness is about 10
-3-10
-4Pa.In order to guarantee CeO
2Fully reduced, under this vacuum tightness, adopt the Frequency Induction Heating mode to carry out temperature increasing for melting materials with 300-500 ℃/hr heat-up rate;
＜5〉the material piece in crucible is warmed up to 1000-1200 ℃ and locates, and in order to make aforesaid equation (1) sufficient reacting, carries out constant temperature 2-3 hour in this temperature range;
＜6〉continue to be warming up to 1900-2000 ℃ with the heat-up rate of 300-500 ℃ of ./hr, wait to expect all fusings after, for the abundant reaction that guarantees raw material and mix, in this temperature range constant temperature 1-2 hour again;
＜7〉in burner hearth, slowly charge into N
2Gas or Ar gas shiled gas make the air pressure of burner hearth remain on 1-1.25atm.Then, at doping trivalent cerium ion (Ce
3+) disilicic acid lutetium high temperature scintillating monocrystal: Lu
2 (1-x-y-z)Re
2xCe
2yM
2zSi
2O
7(wherein Re represents other rare earth element except that Lu, as: one of Y, Gd, Sc, Yb etc. or multiple mixing, M represents metal ions such as Zr, Mg, Ta; 0≤x≤0.3,0.001 under the Tc≤y≤0.05,0.00001≤z≤0.0005) (generally in 1850-1950 ℃ of scope), adopt the cerium ion-doped disilicic acid lutetium high temperature scintillation crystal of technology growth of crystal pulling method, in crystal growing process, adopt pure Lu
2Si
2O
7Seed crystal, the speed of growth are 1-5mm/hr, and the crystal rotating speed is about 10-80RPM.Crystal through sowing, undergauge, shouldering, isometrical, ending, behind the cooling supervisor, crystal growth is finished.
The above-mentioned processing step of the present invention＜4〉described in temperature increasing for melting materials can also adopt graphite heating, perhaps mode such as W heating is carried out temperature increasing for melting materials;
The above-mentioned processing step of the present invention＜7〉described in the crystallization range of cerium ion-doped disilicic acid lutetium scintillation crystal at 1800 ℃-2000 ℃, Tc depends primarily on cerium ion-doped disilicic acid lutetium high temperature scintillation crystal Lu
2 (1-x-y-z)Re
2xCe
2yM
2zSi
2O
7In what of the element of Re representative and content thereof and different, generally the fusing point along with the increase disilicic acid lutetium high temperature crystal of Re constituent content will be reduced to 1850 ℃ from 1950 ℃.
The above-mentioned processing step of the present invention＜7〉described in Lu
2Si
2O
7Seed crystal generally adopts a, b, c is axial or other special crystallization direction carries out crystalline growth.
Below by embodiment preparation process of the present invention is explained, but should not limit its protection domain with this.
Example 1: preparation Lu
1.99798Ce
0.002Zr
0.00002Si
2O
7Disilicic acid lutetium scintillation crystal
According to above-mentioned processing step＜1〉to take by weighing purity respectively by above-mentioned chemical formula be 99.999% exsiccant 0.99899mol Lu
2O
3, 2mol SiO
2, 0.002mol CeO
2, 0.00002mol ZrO
2With 0.00016mol Si
3N
4Raw material, 1500g altogether; By above-mentioned processing step＜2〉the above-mentioned component thorough mixing that takes by weighing is become uniform powder; By above-mentioned processing step＜3〉will mix raw material, under the pressure of 1Gpa, the blended powder is pressed into φ 78 * 10mm
3The material cake, 500 ℃ sintering temperatures 15 hours to remove organism, water and the low melting point impurity in the raw material; By above-mentioned processing step＜4〉go into φ 80 * 60mm with burned material is packaged
3Ir gold crucible in, and in the lifting furnace of packing into, the sealing burner hearth also is evacuated to 5 * 10
-3Pa.Under this vacuum tightness, adopt the Frequency Induction Heating mode to carry out temperature increasing for melting materials with 400 ℃/hr heat-up rate; By above-mentioned processing step＜5〉when the material piece in the crucible is warmed up to 1000 ℃, constant temperature 2.5 hours; By above-mentioned processing step＜6〉continue to be warming up to 2000 ℃ with the heat-up rate of 400 ℃ of ./hr, wait to expect all fusings after, for the abundant reaction that guarantees raw material and mix, constant temperature 1.5 hours in this temperature range again; By above-mentioned processing step＜7〉in burner hearth, slowly charge into N
2Gas makes the air pressure of burner hearth remain on 1.25atm.Under 1950 ℃ of Tcs, adopt the axial Lu of b then
2Si
2O
7Seed crystal adopts Czochralski grown crystal.In crystal growing process, the speed of growth is 2mm/hr, and the crystal rotating speed is about 30RPM.Crystal through sowing, undergauge, shouldering, isometrical, ending, behind the cooling supervisor, crystal growth is finished, and can obtain the indehiscent Lu of φ 35 * 50mm perfect crystalline
1.99798Ce
0.002Zr
0.00002Si
2O
7Water white crystal can be widely used in the fields such as high energy physics nuclear physics and image nuclear medicine.
Example 2: preparation Lu
1.389Ce
0.010Gd
0.6Mg
0.001Si
2O
7Disilicic acid lutetium scintillation crystal
According to processing step＜1 in the foregoing description 1〉by above-mentioned chemical formula Lu
1.389Ce
0.005Gd
0.6Si
2O
7Take by weighing purity respectively and be 99.999% exsiccant 0.6945mol Lu
2O
3, 2mol SiO
2, 0.01mol CeO
2, 0.001mol MgO and 0.00083mol Si
3N
4Raw material, 1500g altogether; Repeat processing step＜2 in the foregoing description 1〉＜3＜4 and＜5; By processing step＜6 in the foregoing description 1〉continue to be warming up to 1980 ℃ with the heat-up rate of 400 ℃ of ./hr, after waiting to expect all to melt, constant temperature is 1.5 hours in this temperature range; By processing step＜7 in the foregoing description 1〉in burner hearth, slowly charge into N
2Gas makes the air pressure of burner hearth remain on 1.25atm.Under 1870 ℃ of Tcs, adopt the axial Lu of b then
2Si
2O
7Seed crystal adopts Czochralski grown crystal.In crystal growing process, the speed of growth is 2.5mm/hr, and the crystal rotating speed is about 40RPM.Crystal through sowing, undergauge, shouldering, isometrical, ending, behind the cooling supervisor, crystal growth is finished.Can obtain the indehiscent colourless transparent crystal of φ 35 * 50mm perfect crystalline at last, can be widely used in the fields such as high energy physics nuclear physics and image nuclear medicine.
Example 3: preparation Lu
1.789Ce
0.010(Y0.5Gd
0.5)
0.2Zr
0.001Si
2O
7Disilicic acid lutetium scintillation crystal
According to processing step＜1 in the foregoing description 2〉by above-mentioned chemical formula Lu
1.789Ce
0.010(Y
0.5Gd
0.5)
0.2Zr
0.001Si
2O
7Take by weighing purity respectively and be 99.999% exsiccant 0.8945mol Lu
2O
3, 2mol SiO
2, 0.01molCeO
2, 0.001mol ZrO
2With 0.00083mol Si
3N
4Raw material, 1500g altogether; Repeat processing step＜2 in the foregoing description 1〉〉＜3＜4 and＜5; By processing step＜6 in the foregoing description 2〉continue to be warming up to 1950 ℃ with the heat-up rate of 400 ℃ of ./hr, after waiting to expect all to melt, constant temperature is 2 hours in this temperature range; By processing step＜7 in the foregoing description 2〉in burner hearth, slowly charge into Ar gas, make the air pressure of burner hearth remain on 1atm.Under 1900 ℃ of Tcs, adopt the axial Lu of b then
2Si
2O
7Seed crystal adopts Czochralski grown crystal.In crystal growing process, the speed of growth is 1mm/hr, and the crystal rotating speed is about 25RPM.Crystal through sowing, undergauge, shouldering, isometrical, ending, behind the cooling supervisor, crystal growth is finished.Can obtain φ 35 * 50mm perfect crystalline disilicic acid lutetium crystal at last, the crystal water white transparency can be widely used in the fields such as high energy physics nuclear physics and image nuclear medicine.
Claims (2)
1, a kind of preparation method who mixes cerium disilicic acid lutetium high temperature scintillating monocrystal is characterized in that this method comprises the following steps:
1. press the chemical formula Lu of doping trivalent cerium ion disilicic acid lutetium
2 (1-x-y-z)Re
2xCe
2yM
2zSi
2O
7Prepare burden, wherein Re represents other rare earth element except that Lu, and M represents Zr, Mg, Ta metal ion; 0≤x≤0.3,0.001≤y≤0.05,0.00001≤z≤0.0005 is behind selected x, y, the z, by the mol ratio of each component oxide correspondence, i.e. Lu
2O
3: Re
2O
3: CeO
2: MO
2: SiO
2=(1-x-y-z): x: 2y: 2z: 2 weighing initial feed, the purity of each initial feed are all greater than 99.99%, and then take by weighing and CeO
2The Si of equivalent mole
3N
4Raw material, the i.e. Si of y/6 mole
3N
4Raw material;
2. each component raw material thorough mixing is become uniform mixed powder;
3. under the pressure of 1-5Gpa, the blended powder is pressed into columned material cake, carried out low-temperature sintering 10-24 hour being lower than under 500 ℃ the temperature;
4. with the packaged Iridium Crucible of advancing in the burner hearth of burned material, or plumbago crucible, or in the tungsten crucible, with the burner hearth sealing and vacuumize, vacuum tightness is about 10
-3-10
-4Pa is in order to guarantee CeO
2Fully reduced, under this vacuum tightness, adopt the Frequency Induction Heating mode to carry out temperature increasing for melting materials with 300-500 ℃/hr heat-up rate;
5. work as Iridium Crucible, or plumbago crucible, or the material piece in the tungsten crucible is warmed up to 1000-1200 ℃ and locates, carried out constant temperature 2-3 hour in this temperature range;
6. continue to be warming up to 1900-2000 ℃ with the heat-up rate of 300-500 ℃ of ./hr, wait to expect all fusings after, in this temperature range constant temperature 1-2 hour again;
7. in burner hearth, slowly charge into N
2Gas or Ar gas make the air pressure of burner hearth remain on 1-1.25atm, then, under the Tc of single crystal of the present invention, generally in 1850-1950 ℃ of scope, adopt the cerium ion-doped disilicic acid lutetium high temperature scintillation crystal of technology growth of crystal pulling method, in crystal growing process, adopt pure Lu
2Si
2O
7Seed crystal, the speed of growth are 1-5mm/hr, and the crystal rotating speed is 10-80RPM, crystal through sowing, undergauge, shouldering, isometrical, ending, behind the cooling supervisor, crystal growth is finished.
2, the preparation method who mixes cerium disilicic acid lutetium high temperature scintillating monocrystal according to claim 1 is characterized in that described Lu
2Si
2O
7The seed crystal direction is axial or other crystallization direction of a, b, c.
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| CN102268734B (en) * | 2010-06-01 | 2013-12-11 | 中国科学院上海硅酸盐研究所 | LPS:Ce luminescent material and preparation method thereof |
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| CN113089096A (en) * | 2019-08-21 | 2021-07-09 | 眉山博雅新材料有限公司 | Crystal |
| WO2021031135A1 (en) * | 2019-08-21 | 2021-02-25 | 眉山博雅新材料有限公司 | Crystals capable of simultaneously detecting neutrons and y/x-rays and preparation method thereof |
| US12018399B2 (en) | 2019-08-21 | 2024-06-25 | Meishan Boya Advanced Materials Co., Ltd. | Crystals for detecting neutrons, gamma rays, and x rays and preparation methods thereof |
| US11827826B2 (en) | 2019-08-21 | 2023-11-28 | Meishan Boya Advanced Materials Co., Ltd. | Methods and devices for growing scintillation crystals |
| US12054848B2 (en) | 2019-08-21 | 2024-08-06 | Meishan Boya Advanced Materials Co., Ltd. | Crystals for detecting neutrons, gamma rays, and x rays and preparation methods thereof |
| CN112062472B (en) * | 2020-08-31 | 2021-12-17 | 华南理工大学 | High-hardness Lu2Si2O7Transparent microcrystalline glass and preparation method thereof |
| CN113176604A (en) * | 2021-04-30 | 2021-07-27 | 中国电子科技集团公司第二十六研究所 | Scintillation crystal array anti-irradiation reinforcing structure and anti-irradiation reinforcing method |
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