CN101723433B - Lanthanum-cerium bromide scintillation crystal - Google Patents
Lanthanum-cerium bromide scintillation crystal Download PDFInfo
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- CN101723433B CN101723433B CN2008101678948A CN200810167894A CN101723433B CN 101723433 B CN101723433 B CN 101723433B CN 2008101678948 A CN2008101678948 A CN 2008101678948A CN 200810167894 A CN200810167894 A CN 200810167894A CN 101723433 B CN101723433 B CN 101723433B
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- 239000013078 crystal Substances 0.000 title claims abstract description 55
- AGONCBOTBXYTGA-UHFFFAOYSA-H cerium(3+) lanthanum(3+) hexabromide Chemical compound [Br-].[Ce+3].[La+3].[Br-].[Br-].[Br-].[Br-].[Br-] AGONCBOTBXYTGA-UHFFFAOYSA-H 0.000 title claims abstract description 13
- 150000002500 ions Chemical class 0.000 claims abstract description 8
- 229910052716 thallium Inorganic materials 0.000 claims description 4
- 238000005728 strengthening Methods 0.000 claims description 3
- 229910052733 gallium Inorganic materials 0.000 claims 1
- 229910052738 indium Inorganic materials 0.000 claims 1
- 229910052706 scandium Inorganic materials 0.000 claims 1
- 239000000126 substance Substances 0.000 claims 1
- 238000000034 method Methods 0.000 abstract description 19
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 abstract description 17
- 239000002994 raw material Substances 0.000 abstract description 15
- 239000010453 quartz Substances 0.000 abstract description 11
- 238000005336 cracking Methods 0.000 abstract description 6
- 238000004519 manufacturing process Methods 0.000 abstract description 6
- 238000002360 preparation method Methods 0.000 abstract description 3
- 239000012744 reinforcing agent Substances 0.000 abstract 3
- 238000009792 diffusion process Methods 0.000 abstract 1
- XKUYOJZZLGFZTC-UHFFFAOYSA-K lanthanum(iii) bromide Chemical compound Br[La](Br)Br XKUYOJZZLGFZTC-UHFFFAOYSA-K 0.000 description 16
- MOOUSOJAOQPDEH-UHFFFAOYSA-K cerium(iii) bromide Chemical compound [Br-].[Br-].[Br-].[Ce+3] MOOUSOJAOQPDEH-UHFFFAOYSA-K 0.000 description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 11
- 238000001816 cooling Methods 0.000 description 10
- 235000012239 silicon dioxide Nutrition 0.000 description 10
- 238000002156 mixing Methods 0.000 description 7
- 239000000463 material Substances 0.000 description 6
- FVAUCKIRQBBSSJ-UHFFFAOYSA-M sodium iodide Chemical compound [Na+].[I-] FVAUCKIRQBBSSJ-UHFFFAOYSA-M 0.000 description 6
- 238000005520 cutting process Methods 0.000 description 5
- 239000002245 particle Substances 0.000 description 5
- 230000002285 radioactive effect Effects 0.000 description 5
- 238000007789 sealing Methods 0.000 description 5
- 229910001622 calcium bromide Inorganic materials 0.000 description 4
- WGEFECGEFUFIQW-UHFFFAOYSA-L calcium dibromide Chemical compound [Ca+2].[Br-].[Br-] WGEFECGEFUFIQW-UHFFFAOYSA-L 0.000 description 4
- 239000007789 gas Substances 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- 238000005086 pumping Methods 0.000 description 4
- 239000000523 sample Substances 0.000 description 4
- KEDNSMBVYXSBFC-UHFFFAOYSA-N 6-bromo-2-chloroquinoline-4-carbonyl chloride Chemical compound C1=C(Br)C=C2C(C(=O)Cl)=CC(Cl)=NC2=C1 KEDNSMBVYXSBFC-UHFFFAOYSA-N 0.000 description 3
- GBLDKMKYYYAAKD-UHFFFAOYSA-K dysprosium(3+);tribromide Chemical compound [Br-].[Br-].[Br-].[Dy+3] GBLDKMKYYYAAKD-UHFFFAOYSA-K 0.000 description 3
- 238000005242 forging Methods 0.000 description 3
- 239000000725 suspension Substances 0.000 description 3
- BKVIYDNLLOSFOA-UHFFFAOYSA-N thallium Chemical compound [Tl] BKVIYDNLLOSFOA-UHFFFAOYSA-N 0.000 description 3
- 229940105965 yttrium bromide Drugs 0.000 description 3
- LSWWNKUULMMMIL-UHFFFAOYSA-J zirconium(iv) bromide Chemical compound Br[Zr](Br)(Br)Br LSWWNKUULMMMIL-UHFFFAOYSA-J 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 238000012856 packing Methods 0.000 description 2
- 230000000704 physical effect Effects 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- 235000009518 sodium iodide Nutrition 0.000 description 2
- 239000006104 solid solution Substances 0.000 description 2
- 238000005303 weighing Methods 0.000 description 2
- 241000024287 Areas Species 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- 238000005275 alloying Methods 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- ORCSMBGZHYTXOV-UHFFFAOYSA-N bismuth;germanium;dodecahydrate Chemical compound O.O.O.O.O.O.O.O.O.O.O.O.[Ge].[Ge].[Ge].[Bi].[Bi].[Bi].[Bi] ORCSMBGZHYTXOV-UHFFFAOYSA-N 0.000 description 1
- XQPRBTXUXXVTKB-UHFFFAOYSA-M caesium iodide Chemical compound [I-].[Cs+] XQPRBTXUXXVTKB-UHFFFAOYSA-M 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- -1 lanthanum bromide cerium ion Chemical class 0.000 description 1
- ADOANNTYRWJJIS-UHFFFAOYSA-N lutetium silicic acid Chemical compound [Lu].[Si](O)(O)(O)O ADOANNTYRWJJIS-UHFFFAOYSA-N 0.000 description 1
- 239000004570 mortar (masonry) Substances 0.000 description 1
- 238000005498 polishing Methods 0.000 description 1
- 238000007517 polishing process Methods 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
- 230000002787 reinforcement Effects 0.000 description 1
- 230000003014 reinforcing effect Effects 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- PBYZMCDFOULPGH-UHFFFAOYSA-N tungstate Chemical compound [O-][W]([O-])(=O)=O PBYZMCDFOULPGH-UHFFFAOYSA-N 0.000 description 1
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- Luminescent Compositions (AREA)
Abstract
The invention relates to a method for manufacturing a lanthanum-cerium bromide scintillation crystal, which is characterized by comprising the following steps of: doping other ions (of a reinforcing agent) during the preparation of a growing raw material of the lanthanum-cerium bromide scintillation crystal to increase the cracking resistance of the crystal, wherein the ions of the reinforcing agent can be trivalent ions, or bivalent or quadrivalent ions; and growing the crystal by adopting a special hanging quartz crucible descent method. Because of the dislocation pinning function of the ions of the reinforcing agent, the method prevents the dislocation diffusion and crystal face slippage, effectively prevents the cracking in the processes of growing and processing the crystal, greatly improves the strength of the prepared lanthanum-cerium bromide scintillation crystal, and improves the quality of the crystal.
Description
Technical field:
The present invention relates to the scintillator crystal materials field, is a kind of lanthanum-cerium bromide scintillation crystal and manufacture method thereof, particularly a kind of preparation method of lanthanum-cerium bromide scintillation crystal of the strengthening agent that can improve the crystal physical strength of having mixed.
Background technology:
Scintillator crystal materials is widely used in the detector that gamma-rays, x ray, Millikan's rays and its energy be higher than above particle of 1kev and ray.
The scintillator crystal materials that has dropped at present industrial application has sodium iodide (thallium), cesium iodide (thallium, sodium), bismuth germanium oxide, plumbous tungstate, silicic acid lutetium etc.On physicals, these scintillator crystal materials respectively have relative merits, also do not have a kind of material can replace all the other materials fully.Therefore, pursuing excellent combination property and cheap scintillation crystal and the preparing process thereof of preparation cost is the target that people struggle all the time.
It is found that in recent years lanthanum bromide, comprise cerium bromide and their mixing sosoloid are very promising novel inorganic scintillators, they have advantages such as photoyield height, response speed is fast, the energy direct ratio is good, application prospect is very big in the working and room temperature gamma spectrometer, at the oil radioactivity well logging, Application Areass such as medical science radiant image also have huge application potential.Existing in the world at present fewer companies can provide the commodity scintillator, but since at present manufacturing process still not mature enough perfect, production cost is very high, cost an arm and a leg, and has limited the industrial application of this kind scintillator greatly.
The difficulty of this crystalloid manufacturing is by the decision of the physical properties of this kind crystal self, this kind crystal is very crisp and very high anisotropy arranged, for example lanthanum bromide is along 6 times of axial 5 ∽ of c along the thermal expansivity of a axle, in crystal growth and follow-up cut mechanically, polishing process, crystal extremely is easy to cracking and broken like this.Manufacturing cost and antidetonation, heat resistanceheat resistant requirement bring in application process application cost have been increased thus greatly.These are restricted its application.
In scintillator intensity reinforcement means in the past, have and adopt forging method, for example sodium iodide (thallium) scintillator can be reinforced with forging method, but the lanthanum bromide crystal is because very hard very crisp, and the scope of its plastic deformation is very little, and the method that forging and pressing are reinforced is impracticable.
The present invention discloses a kind of alloying positively charged ion that adopts and replaces the method for reinforcing lanthanum bromide cerium ion solid solution crystals.By in solid solution lattice, introducing other equivalences or non-equivalence positively charged ion, the original UCl of lanthanum bromide cerium crystal can not changed
3On the basis of structure, produce the sliding motion of local lattice distortion, thereby play the effect of pinning dislocation, make the unlikely cracking of crystal with the prevention dislocation.
Raw materials used is super dried bromide, comprises super dried comprise cerium bromide, lanthanum bromide, Calcium Bromide etc.These can adopt the commercial reagent, and purity is 99.9%-99.99%, and water content must be preferably less than 50ppm less than 100ppm.According to above-mentioned general molecular formula, earlier selected suitable x, y takes by weighing required super dried bromide raw material by corresponding molar percentage again, smashes thin mixing in high-purity agate mortar, and in the special quartz glass tube of packing into.Above raw material weighing, mixing and tubulature all must be carried out in glove box, must keep high dry and pure argon atmospher in the glove box.
The silica tube diameter of above-mentioned loading raw material is to determine according to the diameter of required crystal ingot, be generally Φ 30mm-Φ 100mm, one suspension hook is arranged at its top, it is tapered that the bottom is a tapered rounding, and the drift angle of circular cone is generally 30 °-100 °, preferred 60 °, the bottom is high about 20mm, diameter 5mm-20mm, the cylindrical cavity body of preferred 8mm wherein holds seed crystal (accompanying drawing 1).After installing raw material, silica tube vacuumizes, and sealing is in order to (accompanying drawing 2) growing crystal in the crystal furnace of packing into.
Crystal growth is carried out in two warm area bridgman furnaces, and last warm area design temperature is 800 ℃-900 ℃, and preferred 850 ℃, 650 ℃-750 ℃ of following warm area design temperatures, preferred 700 ℃.Mother tube rests on warm area when slinging beginning in stove, treats that the slow heat temperature raising of long brilliant stove reaches design temperature and 24 hours rears of constant temperature begin to descend.Lowering speed is 0.3-3mm/ hour, and preferred 0.8-1.2mm/ hour, crystal progressively generated in the decline process; Warm area promptly starts cooling process when the crystal that grows into arrives down, and cooling rate is 0.5-5 ℃/hours, and preferred 1 ℃-3 ℃/hour, when reducing near room temperature, furnace temperature can take out long brilliant pipe, and the brilliant process of whole length generally needs 15-20 days.The crystal ingot of having grown is sealed in the aluminum barrel that has quartz window after cutting, grinding, polishing and uses in order to measuring.
Crystal by the open method growth of the present invention has physical strength preferably, and is not easy to crack in the growth and the course of processing, grown the bright crystal of nothing cracking full impregnated of diameter 50mm in this way; And the strengthening agent impurity of introducing generally do not influence the original luminescent properties of scintillator, and in some cases, the luminescent properties of scintillator is improved on the contrary, even is greatly improved.
Adopted the embodiment of the invention to prepare lanthanum-cerium bromide scintillation crystal, volume all can surpass 20cm
3, maximum can reach 100cm
3, whole clearing does not have cracking.Right
137The 662keV photoelectric peak energy resolution of Cs radioactive source all is better than 4.0%.
Description of drawings
The grow long brilliant pipe of quartz of lanthanum-cerium bromide scintillation crystal of Fig. 1
1. quartzy body, 2. suspension hook, 3. bottom reverse taper, the 4. brilliant pipe of length top, 5. seed crystal cavity body, 6. raw material.
Grow two warm area bridgman furnaces of lanthanum-cerium bromide scintillation crystal of Fig. 2
1. go up warm area, 2. descend warm area, 3. long brilliant pipe, 4. suspension hook, 5. stepper-motor, 6. lifting rope, 7. stove silk.
Raw materials used is purity 99.99%, and water content is less than the super dried lanthanum bromide of 100ppm; Purity 99.9%, water content is less than the super dried comprise cerium bromide of 50ppm; Purity 99.99%, water content is less than the super dried yttrium bromide of 100ppm; Lanthanum bromide, comprise cerium bromide are+100 order crystalline particles, and yttrium bromide is a ultrafine powder, and its granularity D50 value is 0.5-5 μ m; Get super dried lanthanum bromide 700 grams, super dried comprise cerium bromide 80 grams, in super dried yttrium bromide 80 restrains the internal diameter Φ 30mm that packs into behind the uniform mixing in the glove box that fills high-purity Ar gas the long brilliant pipe of quartz, the long brilliant pipe of quartz that installs raw material is put into crystal growing furnace and is sling and rest on warm area after vacuum-pumping and sealing, system begins heating then, last warm area heats up with 10 ℃/hour speed, arrive constant temperature behind 820 ℃ of the target temperatures, following warm area heats up with 7 ℃/hour speed, arrive 720 ℃ of later constant temperature of target temperature, last, following warm area all constant temperature after about 24 hours stepper-motor begin to start long brilliant pipe letdown procedure, lowering speed is 1mm/ hour.Treat to begin cooling when long crystal all moves to down in the warm area, the initial stage of cooling, upper and lower warm area was all reduced to 675 ℃ in 24 hours, reduce to room temperature with 2 ℃/hour speed then.Gained crystal ingot entire body is transparent, and cutting is packaged into two Φ 30x30mm scintillators.The scintillation probe that this scintillator and photomultiplier XP2020Q are coupled to form, right
137The 662keV photoelectric peak energy resolution of Cs radioactive source is respectively 3.5% and 3.6%.
Raw materials used is purity 99.99%, and water content is less than the super dried lanthanum bromide of 100ppm; Purity 99.9%, water content is less than the super dried comprise cerium bromide of 50ppm; Purity 99.99%, water content is less than the super dried dysprosium bromide of 100ppm; Lanthanum bromide, comprise cerium bromide, dysprosium bromide are+100 order crystalline particles; Get super dried lanthanum bromide 810 grams, super dried comprise cerium bromide 90 grams, in super dried dysprosium bromide 100 restrains the internal diameter Φ 40mm that packs into behind the uniform mixing in the glove box that fills high-purity Ar gas the long brilliant pipe of quartz, the long brilliant pipe of quartz that installs raw material is put into crystal growing furnace and is sling and rest on warm area after vacuum-pumping and sealing, system begins heating then, last warm area heats up with 10 ℃/hour speed, arrive constant temperature behind 800 ℃ of the target temperatures, following warm area heats up with 7 ℃/hour speed, arrive 700 ℃ of later constant temperature of target temperature, last, following warm area all constant temperature after about 24 hours stepper-motor begin to start long brilliant pipe letdown procedure, lowering speed is 1mm/ hour.Treat to begin cooling when long crystal all moves to down in the warm area, the initial stage of cooling, upper and lower warm area was all reduced to 660 ℃ in 24 hours, reduce to room temperature with 2 ℃/hour speed then.Gained crystal ingot entire body is transparent, gets its stage casing cutting and is packaged into a Φ 40x40mm scintillator.The scintillation probe that this scintillator and photomultiplier XP2020Q are coupled to form, right
137The 662keV photoelectric peak energy resolution of Cs radioactive source is 3.3%.
Raw materials used is purity 99.99%, and water content is less than the super dried lanthanum bromide of 100ppm; Purity 99.9%, water content is less than the super dried comprise cerium bromide of 50ppm; The anhydrous calcium bromide of purity 99.9%; Lanthanum bromide, comprise cerium bromide, Calcium Bromide are+100 order crystalline particles; Get super dried lanthanum bromide 1366 grams, super dried comprise cerium bromide 137 grams, anhydrous calcium bromide 9.6 restrains in the long brilliant pipe of quartz of the internal diameter Φ 50mm that packs into behind the uniform mixing in the glove box that fills high-purity Ar gas, the long brilliant pipe of quartz that installs raw material is put into crystal growing furnace and is sling and rest on warm area after vacuum-pumping and sealing, system begins heating then, last warm area heats up with 10 ℃/hour speed, arrive constant temperature behind 825 ℃ of the target temperatures, following warm area heats up with 7 ℃/hour speed, arrive 725 ℃ of later constant temperature of target temperature, last, following warm area all constant temperature after about 24 hours stepper-motor begin to start long brilliant pipe letdown procedure, lowering speed is 1mm/ hour.Treat to begin cooling when long crystal all moves to down in the warm area, the initial stage of cooling, upper and lower warm area was all reduced to 680 ℃ in 24 hours, reduce to room temperature with 2 ℃/hour speed then.Gained crystal ingot entire body is transparent, gets its stage casing cutting and is packaged into a Φ 50x40mm scintillator.The scintillation probe that this scintillator and photomultiplier XP2020Q are coupled to form, right
137The 662keV photoelectric peak energy resolution of Cs radioactive source is 3.9%.
Raw materials used is purity 99.99%, and water content is less than the super dried lanthanum bromide of 100ppm; Purity 99.9%, water content is less than the super dried comprise cerium bromide of 50ppm; The anhydrous zirconium bromide of purity 99.9%; Lanthanum bromide, comprise cerium bromide, zirconium bromide are+100 order crystalline particles; Get super dried lanthanum bromide 1408 grams, super dried comprise cerium bromide 88.1 grams, in anhydrous zirconium bromide 14.8 restrains the internal diameter Φ 50mm that packs into behind the uniform mixing in the glove box that fills high-purity Ar gas the long brilliant pipe of quartz, the long brilliant pipe of quartz that installs raw material is put into crystal growing furnace and is sling and rest on warm area after vacuum-pumping and sealing, system begins heating then, last warm area heats up with 10 ℃/hour speed, arrive constant temperature behind 840 ℃ of the target temperatures, following warm area heats up with 7 ℃/hour speed, arrive 740 ℃ of later constant temperature of target temperature, last, following warm area all constant temperature after about 24 hours stepper-motor begin to start long brilliant pipe letdown procedure, lowering speed is 1mm/ hour.Treat to begin cooling when long crystal all moves to down in the warm area, the initial stage of cooling, upper and lower warm area was all reduced to 690 ℃ in 24 hours, reduce to room temperature with 2 ℃/hour speed then.Gained crystal ingot entire body is transparent, gets its stage casing cutting and is packaged into a Φ 50x50mm scintillator.The scintillation probe that this scintillator and photomultiplier XP2020Q are coupled to form, right
137The 662keV photoelectric peak energy resolution of Cs radioactive source is 4.0%.
Claims (2)
1. a lanthanum bromide cerium crystal is characterised in that this crystalline chemical general formula is (Ce
xR
yLa
1-x-y) Br
3, 0.01≤x≤0.99,0.01≤y≤0.2,0≤x+y≤1 wherein, R represents+3 valency ion strengthening agents, and it is selected from the combination of a kind of or several elements in Ga, In, Tl, Sc, the Bi group.
2. the described lanthanum bromide cerium crystal of claim 1 is characterised in that its form is the single crystal of whole clearing, and volume is greater than 50cm
3
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| CN2008101678948A CN101723433B (en) | 2008-10-16 | 2008-10-16 | Lanthanum-cerium bromide scintillation crystal |
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| CN102501446A (en) * | 2011-10-31 | 2012-06-20 | 清华大学 | Neodymium-doped lanthanum bromide single crystal flash body and preparing method thereof |
| CN105154973B (en) * | 2015-08-19 | 2017-10-24 | 中国科学院福建物质结构研究所 | Polyion doping large scale lanthanum bromide single crystal flash body and preparation method thereof |
| CN107268068B (en) * | 2017-06-09 | 2018-07-06 | 厦门中烁光电科技有限公司 | The method that lanthanum bromide crystal is prepared using totally enclosed type crucible |
| CN110644047A (en) * | 2019-09-16 | 2020-01-03 | 中国科学院福建物质结构研究所 | Cerium halide-doped magneto-optical crystal, growth method and application thereof |
| CN112817031A (en) * | 2020-12-29 | 2021-05-18 | 北京跃成光子科技有限公司 | Method for efficiently preparing lanthanum-cerium bromide scintillation crystal array |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1404522A (en) * | 2000-02-17 | 2003-03-19 | 科学技术基金会 | Scintillator crystals, method for making same, use thereof |
| CN101070607A (en) * | 2006-05-10 | 2007-11-14 | 宁波大学 | Novel glittering crystal LaBr3Ce3+ crucible-lowering method growth process |
-
2008
- 2008-10-16 CN CN2008101678948A patent/CN101723433B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1404522A (en) * | 2000-02-17 | 2003-03-19 | 科学技术基金会 | Scintillator crystals, method for making same, use thereof |
| CN101070607A (en) * | 2006-05-10 | 2007-11-14 | 宁波大学 | Novel glittering crystal LaBr3Ce3+ crucible-lowering method growth process |
Non-Patent Citations (1)
| Title |
|---|
| P. S. Dutta et al..Growth of gallium antimonide by vertical Bridgman technique with planar crystal-melt interface.《Journal of Crystal Growth》.1994,第141卷44-50. * |
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Effective date of registration: 20170718 Address after: 071000 Wang Zhuang village, Yan Township, Qingyuan District, Hebei, Baoding Patentee after: Hebei Hua Kailong Technology Co., Ltd. Address before: 100085, room 3, building 1, No. ten, 0713 street, Haidian District, Beijing Patentee before: Hao Jia |