CN1060542C - Growth technology of thallium doped cesium iodide crystal by antivacuum fall - Google Patents
Growth technology of thallium doped cesium iodide crystal by antivacuum fall Download PDFInfo
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- CN1060542C CN1060542C CN96116387A CN96116387A CN1060542C CN 1060542 C CN1060542 C CN 1060542C CN 96116387 A CN96116387 A CN 96116387A CN 96116387 A CN96116387 A CN 96116387A CN 1060542 C CN1060542 C CN 1060542C
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Abstract
The present invention relates to a technique for growing thallium-doped cesium iodide crystals by an improved antivacuum descent method, which belongs to the field of cesium iodide crystal growth. When the technical skill provided by the present invention is used, the problem of internal stress in CsI (T1) crystal growth can be overcome, and the present invention is suitable for industrial production. The doped quantity of T1 is from 400 to 800 ppm per 100 g of CsI, and the adding quantity of deoxidizers is from 10 to 500 ppm per 100 g of CsI; a platinum crucible is used for growth, the shape and the dimensions of the crucible can be changed along with growing crystals, and 5 to 20 crystals can grow in the same crucible; the deoxidizing reaction temperature is above the melting point by 50 to 200 DEG C, and the reaction time is from 6 to 8 hours. A cooling rod in a down device is cooled by water in order that the latent heat of crystals can be adjusted and a solid-liquid interface can be controlled.
Description
The present invention relates to descent method one many crucibles of stove growing high-quality cesium iodide,crystal (CsI (T1)) crystalline novel technique, particularly industrialization growing high-quality, large size CsI (T1) crystalline novel process after improving.Belong to cesium iodide crystal growth field.
In recent years the high energy physics field often CsI (T1) crystal as the scintillation material in the electromagnetic calorimeter.Though grown diameter abroad is 9cm, and length is CsI (T1) crystal of 35cm.Usually the method that adopts has: (1) crystal pulling method; (2) kyropoulos; (3) the molten descent method in the directed district of seed crystal and (4) descent method.All these several method common features are CsI (T1) crystal of growing under vacuum condition, and the crucible that growing crystal is used is quartz crucible, and the crystal good for growth quality often uses protective atmosphere.With the breaking of vacuum method is example, uses quartz crucible, adopts vacuum and chemical reaction method to handle raw material removing the hydroxide radical in the raw material, solves in the crystal growing process because of CsI (T1) crystal and quartz crucible adhesion with methods such as top coats to cause crystal cleavage.This method is also complicated to equipment requirements height and raw material treatment technology.Moreover, mix the cesium iodide of T1, be easy to produce wrap, make coloring of crystal at crystal growing process; And T1I a little less than than the Chemical bond power of CsI many, exist T1I to be easy to branch as aerobic and be situated between and be the oxide compound of T1 and I O3-compound, to crystalline flicker give birth to can, especially the anti-radiation performance generation has a strong impact on.
Therefore can be under air atmosphere become that people pay close attention to always and thirst for the Technology that solves, and make the not only anti-light of CsI (T1) crystal that grows hinder the purer CsI of ability can to adopt the suitable industrialization volume production needs of many crucibles growths in the stove by force but also again with Bridgman-Stockbarge method for growing CsI (T1) crystal.
The object of the present invention is to provide a kind of under air atmosphere with descent method for growing large size CsI (T1) crystal and anti-light hinder ability good and in a stove with growing many Technology simultaneously, these Technologies comprise that platinum crucible uses, the adding of reductor, the use of the design of many crucibles growth furnace and water cooling rod.
The raw material that the present invention uses reaches 99.99% CsI (T1) particle premix as purity, and the reductor of every hectogram adding 10-500ppm, is kept at the exsiccant containers for future use after 200 ℃ of vacuum dryings take off OH-.The adding of suitable reductor both can have been removed growing environment and entered oxygen in the melt and also can get rid of trace metal impurity ion in the melt, made to grow crystalline radioresistance injury reinforcing ability and improve greatly.Description (90102951.3,90102828.2 and 93112391.7) is all arranged in these patents of formerly applying for.The reductor that is fit to the present invention's use has iodide such as CHI
3, C
3H
5I; Borate such as Li
2B
4O
7, Na
2B
2O
4And silicate such as Na
2SiO
3, K
2SiO
3Fig. 1 has provided the variation of using with the crystal radioresistance injury reinforcing ability of not using the reductor growth.Abscissa is irradiation dose (rad), and ordinate is relative photoyield.Curve 1 is for adding the anti-irradiation curve of crystal of reductor growth; Curve 2 is anti-irradiation curves of crystal of no reductor growth.Obviously the anti-irradiation ability of the crystal that grows that adds reductor greatly improves.
Second characteristic of the present invention are to adopt platinum as crucible material, utilize the ductility of platinum, have reduced the caused crystal internal stress because crucible expands with heat and contract with cold, and reduce the danger of crystal cleavage, thereby improve the crystalline processed finished products rate that grows.In addition, use platinum crucible can also easily use crystal seed, thereby improve crystalline monocrystalline degree.The preparation process of platinum crucible is described in 94112210.7 applications with requirement.
The 3rd characteristics of the present invention are to adopt the growth furnace of particular design and draw lower device, and its structure as shown in Figure 2.1 is protective tube among the figure, and 2 are the growing crystal platinum crucible, and 3 are heat growth stove globars, and 4 is thermal baffle, and 5 is cooling stick, and 6 are following descending mechanism, and 7 is temperature thermocouple, and 8 is water coolant, and 9 is temperature-control heat couple, and 10 is lagging material.The temperature of one many crucibles of stove growth furnace is controlled with the JWT-702 temperature controller; lagging material 10 is an alumina bubble brick; protective tube 1 is used to protect platinum crucible; can be individual layer or bilayer as growth with platinum crucible; flat rectangular parallelepiped crucible, garden crucible, and different, wall thickness is 0.12-0.20mm with the growing crystal shape; one stove crucible number can between 5-20 only between, to draw cooling stick 5 in the lower device be with the water flowing cooling so as to regulate crystallization latent heat distribute and control solid-liquid interface.
The fusing point of CsI (T1) is 621 ℃, and the every hectogram CsI of the doping of T1 is best between 400-800ppm.Usually carry out deoxygenation and melt being higher than under the fusing point 50-200 ℃ temperature, reaction times is 6-8 hour, the crystal growth gradient is about 35 ℃/cm in the stove, the speed of growth is 1-2.5mm/h, adopt the existing crystallographic orientation of crystal seed, the about 20 ℃/h of blowing out cooling rate, use growth conditions of the present invention and reductor under antivacuum atmosphere, to grow the good crystal of macroscopic quality, this is because use stove of the present invention, the thermograde of the many crucible growths of one stove is greatly stable than vacuum oven, helps the crystalline impurities removal.The present invention grows CsI (T1) crystal, through 103rad
60Behind the Co irradiation, still keep 97% light output.The anti-radiation performance that Fig. 3 lists 3 kinds of different growing crystals compares, and curve 1 is the crystal of the inventive method growth, and 2 is French Q﹠amp; The crystal of S company growth, 3 is Ukraine kharkov crystal, and abscissa is irradiation dose (rad), and ordinate is light output (relatively), and 4 is the anti-irradiation curve of spendable crystalline.Obviously, use method provided by the invention, not only growth conditions is easily gone, and under non-vacuum condition and can be with the many crucibles growths of stove, can reach 20 (look the growing crystal size and different) usually.
In a word, use platinum crucible with this Technology and reduced the crystal internal stress, found suitable reductor to overcome the harm of oxygen to crystal property, improved the anti-irradiation ability of crystalline, many crucible growth reduction production costs have been realized, have work simplification, can realize mass industrialized production high quality large size CsI (T1) crystal easily.
Further set forth substantive distinguishing features of the present invention and obvious improvement below in conjunction with embodiment.
(1) use purity is high-purity CsI (T1) Preblend of 99.99%, and the every hectogram CsI of T1 content is 500ppm, takes off OH-through 200 ℃ of oven dry of vacuum and handles;
(2) growth is 70 * 70 * 550mm with crucible, and wall thickness is 0.12mm;
(3) adopt four straight type globarss, the every limit of burner hearth is established two;
(4) use the water cooling rod, adorn 5 crucibles in the stove;
(5) the melt temperature is 670 ℃, and constant temperature 8 hours carries out deoxygenation;
(6) use CHI
3Be reductor, add-on is 100ppm;
(7) crystalline growth velocity is 1.5mm/ hour, and rate of temperature fall is 20 ℃/hour;
(8) final growing crystal is of a size of 68 * 68 * 360mm.Embodiment 2
(1) reductor is water glass or potassium silicate, and add-on is 300ppm; The every hectogram CsI of T1 add-on is 400ppm;
(2) seeded growth axially is [001];
(3) the melt temperature is 720 ℃, and constant temperature 6 hours uses the flat crucible of 72 * 72 * 550mm, and wall thickness is 0.16mm;
(4) crystal growth rate is 2mm/ hour;
All the other are with embodiment 1, and growing crystal is of a size of 70 * 70 * 350mm, and a stove 5 crucibles is simultaneously grown with stove.
(1) reductor is Li
2B
4O
7Or Na
2B
2O
4, the every hectogram CsI of add-on is 10ppm or 500ppm; The every hectogram of T1 add-on is CsI800ppm in CsI (T1) Preblend;
(2) use the flat platinum crucible of double-deck 72 * 72 * 550mm, wall thickness is 0.12mm;
(3) the material temperature is 770 ℃, and the reaction times is 7 hours;
(4) crystal growth rate is 1mm/ hour.
All the other conditions are with embodiment 1, and growing crystal is of a size of 68 * 68 * 350mm.
Adopt φ 50 flat platinum crucibles in embodiment 1, wall thickness is 0.20mm; Adorn 20 crucibles in one stove and be grown in simultaneously under the antivacuum atmospheric condition and grow, the every hectogram CsI of T1 add-on is 800ppm, and reductor is C
3H
5The I iodide, all the other are with embodiment 1.
Claims (1)
1. the method for the growing thallium doped cesium iodide crystal of antivacuum multi-crucible lowering method comprises the improvement of raw material processing, crucible selection, descent method for growing and growth apparatus and condition, it is characterized in that:
(1) adopting purity is 99.99% CsI (T1) particle premix, and the incorporation of T1 is with every hectogram cesium iodide 400-800ppm, and the reductor that to add every hectogram cesium iodide be 10-500ppm, takes off OH in 200 ℃ of vacuum
-
(2) use has end platinum crucible charging, can be individual layer or double-deck rectangular parallelepiped crucible or garden shape crucible, looks the growing crystal shape and different, and the crucible wall thickness is between 0.12-0.20mm;
(3) be grown in the air atmosphere and carry out, and draw in the lower device cooling stick and adopt the water flowing type of cooling and can grow simultaneously by the many crucibles of a stove, the crucible number is looked crystallographic dimension and different, between 5-20;
(4) high temperature deoxygenation temperature is for being higher than fusing point 50-200 ℃ in the crystal growth, and reaction times 6-8 hour, the growth temperature gradient was 35 ℃/cm, and the speed of growth is 1-2.5mm/ hour, and cooling rate is 20 ℃/hour;
(5) reductor of Shi Yonging can be iodide (CHI
3, C
3H
5I); Silicate (Na
2SiO
3, K
2SiO
3) borate (Li
2B
4O
7, Na
2B
2O
4).
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN96116387A CN1060542C (en) | 1996-06-14 | 1996-06-14 | Growth technology of thallium doped cesium iodide crystal by antivacuum fall |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN96116387A CN1060542C (en) | 1996-06-14 | 1996-06-14 | Growth technology of thallium doped cesium iodide crystal by antivacuum fall |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1199105A CN1199105A (en) | 1998-11-18 |
| CN1060542C true CN1060542C (en) | 2001-01-10 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN96116387A Expired - Fee Related CN1060542C (en) | 1996-06-14 | 1996-06-14 | Growth technology of thallium doped cesium iodide crystal by antivacuum fall |
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Families Citing this family (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE102005034915B4 (en) * | 2005-07-26 | 2012-06-21 | Siemens Ag | Radiation converter and method for producing the radiation converter |
| CN101982568B (en) * | 2010-09-27 | 2012-08-15 | 中国计量学院 | Method for growing strontium iodide scintillating crystals by nonvacuum Bridgman method |
| CN102383195B (en) * | 2011-11-02 | 2015-02-18 | 上海御光新材料科技有限公司 | Bridgman method growth process of cesium iodide and thallium-doped cesium iodide monocrystalline |
| CN102912418B (en) * | 2012-10-18 | 2015-03-04 | 西华大学 | Method and system for growing lead iodide single crystals |
| CN105040091B (en) * | 2015-07-15 | 2019-01-22 | 淮安红相光电科技有限公司 | A kind of sodium chloride optical crystal preparation process and the method for being fabricated to infrared window |
| CN109023504B (en) * | 2018-09-21 | 2020-11-10 | 中国科学院近代物理研究所 | Quartz crucible for growing CsI (Tl) crystal |
| CN111498874B (en) * | 2020-02-21 | 2022-10-04 | 天津大学 | Large-particle-size cesium iodide spherical crystal and preparation method thereof |
| CN113897666A (en) * | 2020-06-22 | 2022-01-07 | 中国科学院上海硅酸盐研究所 | Intrinsically luminous halide scintillation crystal and preparation method and application thereof |
| CN114481320A (en) * | 2020-11-11 | 2022-05-13 | 中国科学院上海硅酸盐研究所 | Method for growing lithium thallium codoped sodium iodide scintillation crystal by non-vacuum Bridgman-Stockbarge method |
| CN115029770B (en) * | 2021-03-04 | 2024-05-03 | 北京一轻研究院有限公司 | Crucible atmospheric lowering furnace device and method |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6028604A (en) * | 1983-07-27 | 1985-02-13 | Toshiba Corp | Manufacture of light transmitting material |
-
1996
- 1996-06-14 CN CN96116387A patent/CN1060542C/en not_active Expired - Fee Related
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6028604A (en) * | 1983-07-27 | 1985-02-13 | Toshiba Corp | Manufacture of light transmitting material |
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| CN1199105A (en) | 1998-11-18 |
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