CN103789832B - For growing nested type crucible and the method for growth strontium iodide crystal of strontium iodide crystal - Google Patents
For growing nested type crucible and the method for growth strontium iodide crystal of strontium iodide crystal Download PDFInfo
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Abstract
The present invention relates to the nested type crucible for growing strontium iodide crystal and the method for growth strontium iodide crystal, described nested type crucible includes the inner crucible for accommodating crystal growth raw material and for providing the outer crucible of the vacuum-pumping of sealed environment, wherein said outer crucible is silica crucible, and described inner crucible is Metal Substrate crucible or carbon back crucible；Described outer crucible is longer than described inner crucible, can surround described inner crucible after sealing by fusing completely；Spacing between outer wall and the inwall of described outer crucible of described inner crucible is not less than 0.6mm.The nested type crucible of the present invention combines silica crucible, Metal Substrate and the advantage of carbon back crucible, effectively eliminates the inferior position of each of which, such that it is able to for high-quality undoped and the growth of doping strontium iodide crystal.
Description
Technical field
The present invention relates to a kind of crucible for growing strontium iodide crystal and the method for growth strontium iodide crystal, be specifically related to one
Plant nested type crucible and the method using this nested type crucible growth strontium iodide crystal, belong to technical field of crystal growth, particularly
Halide crystal growing technology field.
Background technology
Inorganic scintillator can be used for quickly, determines highly enricked uranium, weapons grade plutonium, radioactive source and other spy sensitively and accurately
The gamma-rays characteristic of different nuclear fuel material, in Radionuclides identification, safety inspection, environmental monitoring, chemical and biological weapons verification, mental retardation
The radiation detection fields such as nuclear test and nuclear non-proliferation verification have a wide range of applications.In recent years, along with whole world nuclear safety and terror
Situation increasingly serious, and the raising of people's Radiation Environment Safety consciousness, increase the most day by day to the demand of higher performance scintillator
Add.At present, a kind of scintillator being most widely used in above-mentioned field is NaI:Tl crystal, but the energy of NaI:Tl crystal
Response disproportional and energy resolution poor-performing, and as the hypertoxic Tl of activator ion+A large amount of uses of ion, also deposit
In the potential safety hazard that environment is contaminated.A new generation scintillation material LaBr3: Ce crystal has a good scintillation properties, but this material
There is serious cleavage or stress cracking in material, melt easily reacts with crucible, and raw material and preparation cost are the highest, with
Time possibly together with producing radioactive background138La isotopic composition, its application in radiation detection field receives bigger
Limit.
As far back as 1969, U.S. Robert Hofstadter just applied for Eu2+Doping strontium iodide (SrI2: Eu) crystal conduct
The patent of radiation detection material, but owing to preparing the second-rate of crystal at that time, performance is compared to the most business-like Tl+From
Son doping NaI crystal there is no advantage, and its correlational study is absorbed in the silence of nearly 40 years subsequently.Until 2008, in state of the U.S.
Under department outlay such as soil security bureau and Ministry of Energy etc. is supported, preparing high-quality SrI2: after Eu crystal, Nerine Cherepy
Et al. re-recognize SrI2: the excellent scintillation properties of Eu, strontium iodide is led by inorganic scintillator the most again as a kind of scintillator
The attention in territory, associated research rapidly becomes inorganic scintillator study hotspot and forward position.Their research shows, SrI2:Eu
Light export up to 120,000ph/MeV, be the known light the highest inorganic scintillator of output, there is splendid energy resolution
(< 3%), there is in wider energy range preferable energy linearity.It addition, strontium iodide has relatively low fusing point
(538 DEG C), without cleavage, from melting temperature to room temperature in the range of without phase transformation, easily use Bridgman-Stockbarger method realize scale,
Prepared by industrialization.
In Bridgman-Stockbarger method prepares crystallization process, crucible is to hold the container with melt raw material, is also the appearance of crystal growth
Device, high-temperature fusant directly contacts with crucible, therefore its shape, size, structure and physicochemical characteristic to grow crystal quality,
Size and performance have a great impact.
Strontium iodide is alkaline-earth halide, easy deliquescence and oxidation, and the most frequently used crucible of current crystal growth is quartz earthenware
Crucible, by anhydrous high-purity SrI2And EuI2Raw material loads silica crucible, by silica crucible after evacuation after weighing mixing in proportion
Sealing by fusing, carries out crystal growth under air atmosphere.After evacuation sealing by fusing, it is achieved growth raw material is complete with the environment in the crucible external world
Full isolation.But select silica crucible growth strontium iodide, there is also certain problem: on the one hand, the thermal expansion system of silica crucible
Number (0.6 × 10-6℃-1) and strontium iodide Thermal Expansion in Crystals coefficient (0.9-2.1 × 10-5℃-1) there is bigger difference, raw at crystal
In growth process, crystals can accumulate bigger stress, often occurs the phenomenon of crystal cleavage in crystal growth or temperature-fall period；
Still further aspect, experimental studies have found that, the melt of strontium iodide is often had an effect with silica crucible so that occur inside silica crucible
Corrosion, forms one layer of duricrust growing plane of crystal, crucible can be made time serious to burst, and this has a strong impact on and grows crystalline substance
The quality of body and performance, even result in crystal growth failure.
The crucible of Metal Substrate, the crucible made such as single metal such as aluminum, platinum, iraurite, tungsten and molybdenum, or by two kinds or two
Plant the crucible that the alloy of above metal makes, if selecting properly, it is possible to avoid the reaction of melt and crucible material, and due to gold
Belong to base crucible and typically there is preferable ductility, the stress assembled in crystal growing process can be substantially reduced, can be significantly
Reduce the probability of crystal cleavage；Additionally Metal Substrate crucible has easy to process, the feature of repeatable utilization, is suitable for large scale brilliant
Prepared by the mass of body.Qin Laishun et al. has applied for the patent of employing antivacuum Bridgman-Stockbarge method for growing strontium iodide method, by deoxidation
Agent and raw material are positioned in metallic crucible, use Bridgman-Stockbarge method for growing after being sealed by metallic crucible.But the shortcoming of Metal Substrate crucible
It is the evacuation process that cannot use similar silica crucible method, is usually under zero relative pressure, carries out flame welding seal operation,
Welding inevitably introduces oxygen and hydrone, typically can dose deoxidizer and build the internal medium of a weak reduction, deoxidation
The introducing of agent brings new challenge to crystal growth；It addition, when melt is under high temperature, crucible internal pressure is very big, easily
Cause crucible to burst, cause environment to completely cut off complete failure, cause crystal growth failure.
The crucible of carbon back, such as graphite crucible or vitreous carbon crucible, has preferable chemical stability, can design effective
Eliminate structure, and typically do not react with raw material, but this class crucible cannot realize preferably sealing, and is usually used in unsealed
Breaking of vacuum method growth halide crystal, such as BaF2、CeF3、MgF2Deng.During unsealed breaking of vacuum method, need
Will be to crucible, heating and heat-insulation system pumping high vacuum incessantly, equipment is the hugest；It addition, it is brilliant for general halogenide
For bulk-growth, melt can be caused acutely to volatilize, volatile matter also can produce large effect to vacuum system and external environment.
Summary of the invention
The problem existed in the face of prior art, it is an object of the invention to provide a kind of simple to operate, with low cost, applicable
The method of the nested type crucible growth strontium iodide crystal of mass, to realize this crystal-like industrialized production.
The pluses and minuses being respectively arranged with for silica crucible, Metal Substrate and carbon back crucible, present invention recognize that if preferably merging three
The advantage of person, and it is effectively reduced or eliminates the inferior position of each of which, it is expected to open up one effectively for the growth of strontium iodide crystal
Approach.
Here, on the one hand, the present invention provides a kind of nested type crucible for growing strontium iodide crystal, described nested type earthenware
Crucible includes the inner crucible for growing crystal and for providing the outer crucible of the vacuum-pumping of sealed environment, wherein said outer layer
Crucible is silica crucible, and described inner crucible is Metal Substrate crucible or carbon back crucible；Described outer crucible is than described inner crucible
It is long, so that described inner crucible can be surrounded after sealing by fusing completely；The inwall of the outer wall of described inner crucible and described outer crucible it
Between spacing not less than 0.6mm, preferably 0.6～1mm.
The nested type crucible of the present invention combines silica crucible, Metal Substrate and the advantage of carbon back crucible, effectively eliminates them
Respective inferior position, such that it is able to for high-quality undoped and the growth of doping strontium iodide crystal.Wherein, provided by the present invention
Metal Substrate/quartz nested type crucible, both avoided the component volatilization impact on pumped vacuum systems, inhibit again melt with quartz
The reaction of crucible, the size and dimension growing crystal is easily controlled, and crystal stress is little, the most easy to crack, and the crystal grown is complete
Whole property is good, and the yield rate of growth is high, is suitable for industrialized production.It addition, carbon back provided by the present invention/quartz nested type earthenware
Crucible combine carbon back easily design superseded structure, eliminate success rate high, not with the advantage of fusant reaction, and the easy sealing by fusing of silica crucible
Feature, crystal growing process crucible under air atmosphere can decline in stove and complete, it is to avoid huge fine vacuum growth sets
Standby use, the volatilization of melt has obtained farthest limiting, has had simple in construction, it is easy to mass and industrialized spy
Point.
It is preferred that the bottom of described inner crucible is formed as the structure with spontaneous superseded function.As such, it is possible at crystal
Without using seed crystal in growth course.
It is preferred that the SiO of described silica crucible2Content be not less than 99.99%.
It is preferred that the material of described Metal Substrate crucible is any one metal in aluminum, platinum, iridium, tungsten and molybdenum or any two
Plant the alloy of above metal.
It is preferred that described carbon back crucible is graphite crucible or vitreous carbon crucible.
On the other hand, the present invention provides a kind of method using above-mentioned nested type crucible growth strontium iodide crystal, including:
(1) in humidity is not higher than the environment of 5%, the crystal growth raw material containing high-purity strontium iodide and high-purity adulterant is loaded above-mentioned embedding
In the inner crucible of shell type crucible；
(2) under vacuum described crystal growth raw material is heated to 300～450 DEG C, and is incubated 2～20 hours and carries out pre-place
Reason；
(3) when keeping evacuation, the nested type crucible filling pretreated raw material is cooled to room temperature, sealing by fusing outer layer earthenware
Crucible；And
(4) the nested type crucible after sealing by fusing is inserted crucible degrowth stove, carry out crystal growth by Bridgman-Stockbarger method.
The present invention uses nested type crucible, by Bridgman-Stockbarge method for growing strontium iodide crystal, simple to operate, equipment is wanted
Ask low, with low cost, be suitable for mass, it is possible to achieve high-quality undoped and the industrialized production of doping strontium iodide crystal.
By using the metal/quartz nested type crucible growth strontium iodide crystal of the present invention, both avoided component volatilization to pumped vacuum systems
Impact, the reaction of suppression melt and silica crucible again, the size and dimension growing crystal is easily controlled, and crystal stress is little,
The most easy to crack, the crystal perfection grown is good, and the yield rate of growth is high, is suitable for industrialized production.By using the present invention
Carbon back/quartz nested type crucible growth crystal, combine carbon back easily design superseded structure, eliminate success rate high, not with melt
The advantage of reaction, and the feature of the easy sealing by fusing of silica crucible, crystal growing process can decline in stove by the crucible under air atmosphere
Completing, it is to avoid the use of huge fine vacuum growth apparatus, the volatilization of melt obtained farthest suppressing, had structure
Simply, with low cost, be prone to mass and industrialized feature.
It is preferred that in step (1), described humidity is not higher than the environment of 5% and is preferably water and oxygen content is all not higher than
The inert ambient environment of 1000ppm.
It is preferred that in step (2), described vacuum condition is that vacuum is not higher than 0.1Pa.Preferably, vacuum is
10-3Below Pa.
It is preferred that in step (1), Eu can be used2+、Eu3+、Tl+、Pb2+、Yb2+And Yb3+Isoionic iodate
Thing, bromide, chloride or fluoride etc. are as adulterant, and doping content can be 0～10at%, and optimal doping is dense
Spend relevant with doping ionic species；Also adulterant, the strontium iodide crystal of growth undoped can not be used.
It is preferred that in step (4), described crystal growth comprises the following steps: little 550～700 DEG C of insulations 2～10
Time fusing crystal growth raw material；Control growth interface thermograde at 10～60 DEG C/cm, with 0.1～the speed of 5.0mm/ hour
Decline crucible and carry out crystal growth；Crystal growth terminates rear furnace temperature and reduces by 50～100 DEG C, makes crystal and crucible anneal in position
1～20 hour；And naturally cool to room temperature after cooling to 100 DEG C with the speed of 10～50 DEG C/h.
It is preferred that in crystal growth, it is possible to use seed crystal carries out inoculation growth, it is possible to use spontaneous nucleation growth.
Accompanying drawing explanation
Fig. 1 is the structural representation of the crucible degrowth stove employed in one example of the present invention；
Fig. 2 is the structural representation of the quartz/platinum nested type crucible eliminating structure with capillary of one example of the present invention；
Fig. 3 is the structural representation of the seed crystal inoculation growth quartz/platinum nested type crucible of one example of the present invention；
Fig. 4 is the structural representation with the compound quartz/graphite nested type crucible eliminating structure of one example of the present invention.
Detailed description of the invention
The present invention is further illustrated, it should be appreciated that accompanying drawing and following embodiment are only below in conjunction with accompanying drawing and following embodiment
For the present invention is described, and the unrestricted present invention.In the accompanying drawings, identical key element is marked with identical symbol and omission repeats
Bright.
Fig. 1 illustrates the structural representation carrying out crystal growth used crucible degrowth stove in one example of the present invention.As
Shown in Fig. 1, this growth furnace mainly includes that temperature field controls device and crystal growing apparatus.Wherein temperature field control device can include protecting
Temperature brick 1 and the heater 2 being arranged in insulating brick 1.Heater 2 can use metal or alloy heating rod, wherein with
Si-Mo rod is the most commonly used.By selecting different insulating bricks in zones of different and arranging the heater 2 position in insulating brick 1
Put, growth furnace can be arranged in vertical direction have uniform temperature distribution, be in turn divided into the most from top to bottom high-temperature region,
Gradient zones and low-temperature space.The fusing of crystal growth raw material is carried out in high-temperature region；Crystal growth is carried out in gradient zones.Additionally, protecting
Near heater 2 in temperature brick 1, temperature-control heat couple 3 can also be set, to control the temperature in this region.Temperature-control heat couple 3 example
As platinum rhodium 10-platinum thermocouple (S type thermocouple) can be used.Should be understood that the warm field of above-mentioned example controls device merely to say
The working environment of the nested type crucible of the bright present invention, and the unrestricted present invention.
<nested type crucible>
Crystal growing apparatus mainly includes nested type crucible 4.Single or multiple nested type crucible 4 can be placed in growth furnace.It addition,
Temperature thermocouple 5 can also be set in the bottom of nested type crucible 4 to monitor crystal growth temperature in real time.Also, nested type crucible
4 can be supported with support crucible 6.
Fig. 2～4 illustrates the structural representation of the nested type crucible of three examples of the present invention.As shown in figs. 2 to 4, nested type
Crucible 4 includes inner crucible 7,7A, 7B and outer crucible 8.Inner crucible 7,7A, 7B are used for holding and melt former
Material, and for crystal growth.In one example, inner crucible 7,7A, 7B are Metal Substrate crucible, and its material can be
Single metal such as aluminum, platinum, iridium, tungsten and molybdenum etc., it is also possible to be the alloy of two or more metal.In another example
In, inner crucible 7,7A, 7B are carbon back crucible, can be graphite crucible or vitreous carbon crucible.Inner crucible 7,
Depending on the size and shape of 7A, 7B can be according to the size and shape of crystal to be grown.Such as its shape can be cylinder,
The shapes such as round platform, circular cone, cuboid, prismoid shaped or prism.Also, inner crucible can be that bottom is with spontaneous superseded function
Crucible shape.Especially when inner crucible uses carbon back crucible, it is easy to structure is eliminated in design.In the illustrated example shown in fig. 2,
The bottom of inner crucible 7 has capillary and eliminates structure 9.The internal diameter of wicking portion can be the 1/15～1/8 of upper inner diameter, length
Can be the 1/6～1/3 of crucible overall length.In the example depicted in fig. 4, the bottom of inner crucible 7B has compound superseded structure
9B.This compound bottom eliminating structure 9B and top are capillary structure, and middle part is the structure of cone.By means of this, can
To form the fewest nucleus in the capillary structure of bottom, and these nucleus are superseded through amplifying again, finally enter top and eliminate
Structure is eliminated again, and the good nucleus of remaining orientation occupies whole melt and develops into crystal.The bottom of inner crucible 7 is all right
It is configured to the structure of fixing seed crystal, such that it is able to be applicable to be carried out the situation of inoculation growth by seed crystal.Such as Fig. 3's
In example, seed crystal 10 can be fixed in the bottom of inner crucible 7A.Seed crystal can be directed to or non-directional, the most optional [010],
[100], the seed crystal of [001] and any direction carries out inoculation growth.Inner crucible 7,7A, 7B can be sealed bottom, top
The structure of portion's opening, it is also possible to be the structure of bottom and the equal opening in top.When its bottom opening, can with outer crucible 8 altogether
Use its bottom surface.
Owing to strontium iodide is alkaline-earth halide, easy deliquescence and oxidation, therefore its environment of crystal growth is preferably vacuum ring
Border.In the present invention, by the outer crucible 8 of sealing by fusing the vacuum environment of sealing can be provided.Outer crucible 8 can be quartz
Crucible.Preferably, its SiO2Content be not less than 99.99%.Outer crucible 8 can be sealed bottom, open-topped knot
Structure.Preferably, inner crucible 7,7A, 7B can put into from the open top of outer crucible 8, take out.Ectonexine crucible
Can share or not share same crucible bottom surface.Outer crucible 8 is longer than inner crucible 7,7A, 7B.Also, outer crucible 8
Open top can be with sealing by fusing.Outer crucible 8 can surround inner crucible 7,7A, 7B after sealing by fusing completely, thus is interior
Crystal growth in crucible 7,7A, 7B provides the vacuum environment sealed.It addition, inner crucible 7, the outer wall of 7A, 7B
And the spacing between the inwall of outer crucible 8 is preferably not less than 0.6mm, preferably 0.6～1mm, so may be easy to put
Enter, take out inner crucible 7,7A, 7B, and the thermal expansion for inner crucible 7,7A, 7B provides space.Outer crucible 8
Shape do not limit, as long as inner crucible 7,7A, 7B can be placed and it is surrounded completely, such as, can be cylinder
The shapes such as body, round platform, circular cone, cuboid, prismoid shaped or prism.
<crystal growth>
In the present invention, above-mentioned nested type crucible can be used to carry out crystal growth.Specifically, as example, crystal growth can include
Following steps.
1) charging: crystal growth raw material is loaded the inner crucible of nested type crucible.When crystal to be prepared is undoped iodine
When changing strontium crystal, can select high-purity strontium iodide (such as purity is more than 99.99%) is raw material.When crystal to be prepared is
During doping strontium iodide crystal, high-purity strontium iodide (such as purity is more than 99.99%) can be selected and high-purity adulterant is (such as
Purity is more than 99.99%) it is raw material.The adulterant used can be Eu2+、Eu3+、Tl+、Pb2+、Yb2+And Yb3+Deng
The iodide of ion, bromide, chloride or fluoride etc..Doping content can be 0～10at%, optimal doping content
Relevant with doping ionic species.Charging process preferably completes in the environment of humidity not higher than 5%.Such as can contain at water and oxygen
Amount is carried out in being all not higher than the inert-atmosphere glove box of 1000ppm.Furthermore it is possible to as required at internal layer earthenware before charging
Seed crystal is put into carry out inoculation growth bottom crucible.Seed crystal can be directed to or non-directional.Such as can select [010], [100], [001]
And the seed crystal of any direction carries out inoculation growth.Also, seed crystal can not also be put into, and use the special-shaped spontaneous superseded life of crucible
Long, may be variant on the crystal mass now grown.The size and shape of inner crucible can be by required growth crystal
Shape, size are selected.Also, multiple nested type crucible can be selected simultaneously, to grow difformity (as cylindrical, long simultaneously
Square etc.), different size and the SrI of heterogeneity2Crystal.
2) pretreatment of raw material: under certain temperature schedule and vacuum, carries out heat pre-treatment to the raw material loaded.Example
As, make vacuum be not higher than 0.1Pa, be preferably 10 keeping external crucible evacuation-3Under the state of below Pa, by raw material
It is heated to 300～450 DEG C, and is incubated 2～20 hours, to remove water possible in raw material and fugitive constituent.
3) crucible sealing by fusing: keep step 2) in evacuation state, will fill pretreated raw material nested type crucible fall
As little as room temperature, the outer crucible of sealing by fusing.Oxyhydrogen flame welding torch such as can be used to carry out sealing by fusing.As such, it is possible to make following crystal growth
Process is carried out in airtight vacuum environment.
4) crystal growth: nested type crucible after sealing by fusing is inserted crucible degrowth stove, starts to warm up, be incubated and melt former
Material, controls certain furnace temperature and temperature gradient of solid-liquid interface so that crucible, enters by temperature gradient zone with certain fall off rate
Row crystal growth.Such as, specifically can use following steps: first by Control for Kiln Temperature in the range of 550～700 DEG C, insulation 2～
10 hours, melt all raw materials, seed crystal top can also be melted when using seed crystal；Growth interface thermograde controls
At 10～60 DEG C/cm, preferably 30～40 DEG C/cm, with 0.1～the speed of 5.0mm/ hour (preferably 0.2～2mm/ hour)
Declining crucible makes raw material pass through temperature gradient zone to grow crystal；After all raw materials are all by temperature gradient zone, stop under crucible
Fall, growth terminates.After growth terminates, temperature control is reduced by 50～100 DEG C so that crystal and crucible are annealed 1～20 little in position
Time；Then, cool to 100 DEG C with the speed of 10～50 DEG C/h (preferably 10～20 DEG C/h), close growth furnace electricity
Source, naturally cools to room temperature.The strontium iodide crystal that growth obtains can take out in an inert atmosphere.Can be first by nested type crucible
Outer crucible opening or destruction, take out inner crucible, peel off inner crucible, i.e. can get strontium iodide crystal.
The invention have the advantage that the use of Metal Substrate/quartz nested type crucible, both avoided component volatilization, and suppressed again melt
With the reaction of silica crucible, the size and dimension growing crystal is easily controlled, and crystal stress is little, the most easy to crack, grows
Crystal perfection is good, and the yield rate of growth is high, is suitable for industrialized production.It is easy that carbon back/quartz nested type crucible combines carbon back
Design eliminate structure, eliminate success rate high, not with the advantage of fusant reaction, and the feature of the easy sealing by fusing of silica crucible, crystal is raw
Growth process can under air atmosphere under crucible decline in stove and complete, it is to avoid the use of huge fine vacuum growth apparatus, molten
The volatilization of body has obtained farthest limiting, and has simple in construction, it is easy to mass and industrialized feature.
Enumerate embodiment further below to describe the present invention in detail.It will similarly be understood that following example are served only for this
Bright it is further described, it is impossible to being interpreted as limiting the scope of the invention, those skilled in the art is according to the present invention's
Some nonessential improvement and adjustment that foregoing is made belong to protection scope of the present invention.The technique ginseng that following example is concrete
Number etc. is the most only an example in OK range, in the range of i.e. those skilled in the art can be done suitably by explanation herein
Select, and do not really want to be defined in the concrete numerical value of hereafter example.
Embodiment 1
Use platinum/quartz nested type crucible, the spontaneous pure SrI of superseded growth2The concrete technology step of crystal is:
1) making capillary platinum crucible, platinum crucible internal diameter is 25mm, and platinum crucible thickness is 0.1mm, and platinum crucible bottom is
Having the capillary structure of spontaneous superseded function, wicking portion internal diameter is 2-3mm, a length of 40mm, and platinum crucible overall length is
200mm, it is 30mm silica crucible that above-mentioned platinum crucible is placed in internal diameter, the tubular silica crucible of a length of 320mm
In, form platinum/quartz nested type crucible；
2) in nitrogen inert-atmosphere glove box, 200g strontium iodide raw material (purity is not less than 99.99%) is loaded quartz/platinum embedding
In shell type crucible (as shown in Figure 2)；
3) the nested type crucible that will be equipped with strontium iodide raw material takes out from glove box, to outer layer silica crucible evacuation, and gradually rises
Temperature is to 450 DEG C, and keeps 10h to remove possible water and fugitive constituent in raw material in this temperature, is incubated in above-mentioned liter gentleness
Cheng Zhong, in crucible, vacuum remains at below 0.01Pa；
4) keep the state to silica crucible evacuation, use oxyhydrogen flame welding torch by outer layer silica crucible sealing by fusing；
5) in the single crystal growing furnace of structure as shown in Figure 1, the bottom of quartz good for sealing by fusing/platinum nested type crucible is placed in diagram growth furnace
Middle and upper part, temperature gradient zone, temperature control is 600 DEG C so that in crucible, whole raw materials (including capillary end) all melt, solid-liquid circle
The gradient of surface temperature maintains 40 ± 2 DEG C/about cm, declines crucible with 0.6mm/h speed, treats that all raw materials all pass through temperature
Behind gradient zones, stopping crucible and decline, growth terminates；
6) temperature control is down to 450 DEG C, and keeps this temperature 10h that crystal carries out in-situ annealing, then drop to the speed of 30 DEG C/h
100 DEG C, then close heating power supply so that natural crystal is cooled to room temperature；
7) in the glove box of nitrogen atmosphere, the outer layer silica crucible of nested type crucible is destroyed, take out internal layer platinum crucible, peel off
Platinum crucible, obtains the undoped strontium iodide crystal of diameter 25mm.
Embodiment 2
Use seed crystal inoculating process, platinum/stone nested type crucible grows SrI2: the processing step of Eu crystal is:
1) by the SrI of 250g2(purity is not less than 99.99%) and the EuI of 8.913g2(purity is not less than 99.9%) powder body conduct
Raw material, is below in the inert-atmosphere glove box of 100ppm at water and oxygen content, by raw material mix homogeneously good for proportioning；
2) in above-mentioned glove box, a diameter of 10mm processed, the strontium iodide seed crystal of a length of 60mm is placed in makes platinum
The bottom of gold crucible, fixes seed crystal, then puts into mixed raw material M1 in silica crucible, as shown in Figure 3；
3) platinum crucible installing raw material is put in quartz glass tube, nested type crucible is taken out from glove box, after raw material is heated
Carrying out pretreatment, in making crucible in processing procedure, vacuum is maintained at below 0.01Pa；
4) in the crucible shown in Fig. 1 declines stove, temperature control, at 650 DEG C, raises platinum/quartz nested type crucible and makes seed crystal top section
Melted, growth interface thermograde maintains 35 DEG C/about cm, declines crucible with 0.2mm/h speed, until melt all leads to
Excess temperature gradient zones crystallizes；
5) after growth terminates, temperature control is reduced to 500 DEG C, is incubated 10h, crystal is carried out in-situ annealing process, then with 30 DEG C/h
Speed drop to 100 DEG C, then close heating, be naturally cooling to room temperature；
6) in glove box, outer layer silica crucible is destroyed, take out the platinum crucible of internal layer, and then peel off platinum crucible, take out complete
SrI2: 3at%Eu crystal.
Embodiment 3
Graphite/silica crucible is used to grow pure SrI2The concrete technology step of crystal is:
1) making graphite/quartz nested type crucible as shown in Figure 4, wherein graphite crucible has combined type and eliminates structure and design；
2) in above-mentioned graphite/quartz nested type crucible, it is gradually added strontium iodide (purity is 99.99%) the raw material M2 of 100g,
Carrying out evacuation and heat treatment, when keeping vacuum to be better than 0.01Pa, be progressively warmed up to 400 DEG C, then constant temperature is extremely
Few more than 2 hours, thermostatic process remains in that and is better than≤the vacuum of 0.01Pa, stop heat treatment afterwards and keeping true
It is down to room temperature in the case of reciprocal of duty cycle is constant；
3) by the outer layer silica crucible sealing by fusing of graphite/quartz nested type crucible, during sealing by fusing, in making crucible, vacuum is maintained at
≤0.1Pa；
4) in the crucible shown in Fig. 1 declines stove, temperature control, at 650 DEG C, raises quartz/graphite nested type crucible and makes seed crystal top section
Melted, growth interface thermograde maintains 35 DEG C/about cm, declines crucible with 0.5mm/h speed, until melt all leads to
Excess temperature gradient zones crystallizes；
5) after growth terminates, temperature control is reduced to 500 DEG C, is incubated 10h, crystal is carried out in-situ annealing process, then with 30 DEG C/h
Speed drop to 100 DEG C, then close heating, be naturally cooling to room temperature；
6) in glove box, outer layer silica crucible is destroyed, take out the platinum crucible of internal layer, and then peel off platinum crucible, take out complete
Undoped SrI2Crystal.
For ease of fully understanding the present invention, in example above illustrates, give some concrete ins and outs and processes, but
Being that the present invention can also use other alternate manner being different from this description to implement, those skilled in the art can be without prejudice to this
Similar expansion is done in the case of invention intension.When illustrating the embodiment of the present invention, for purposes of illustration only, process and the description of details
Carry out in conjunction with embodiment crucible structure figure, but during the actual fabrication of crucible, its physical dimension and shape can roots
According to being actually needed free change.
Industrial applicability: the present invention provides the nested type crucible growth of a kind of simple to operate, with low cost, applicable mass
The method of strontium iodide crystal, it is possible to achieve this crystal-like industrialized production.Undoped prepared by the present invention and doping strontium iodide
Scintillation crystal is applicable to the fields such as Security Inspection Equipments, nuclear medicine and radiation detection.
Claims (13)
1. the nested type crucible being used for growing strontium iodide crystal, it is characterized in that, including for accommodating the inner crucible of crystal growth raw material and for providing the outer crucible of the vacuum-pumping of sealed environment, wherein said outer crucible is silica crucible, and described inner crucible is Metal Substrate crucible or carbon back crucible；
Described outer crucible is longer than described inner crucible, can surround described inner crucible after sealing by fusing completely；
Spacing between outer wall and the inwall of described outer crucible of described inner crucible is not less than 0.6mm；
The bottom of described inner crucible has compound superseded structure, and this compound bottom eliminating structure and top are capillary structure, and middle part is the structure of cone.
Nested type crucible for growing strontium iodide crystal the most according to claim 1, it is characterised in that the SiO of described silica crucible2Content be not less than 99.99%.
Nested type crucible for growing strontium iodide crystal the most according to claim 1 and 2, it is characterised in that the material of described Metal Substrate crucible is any one metal in aluminum, platinum, iridium, tungsten and molybdenum or the alloy of any two or more metal.
Nested type crucible for growing strontium iodide crystal the most according to claim 1 and 2, it is characterised in that described carbon back crucible is graphite crucible or vitreous carbon crucible.
5. the method growing strontium iodide crystal, it is characterised in that including:
(1) in humidity is not higher than the environment of 5%, the crystal growth raw material containing high-purity strontium iodide and high-purity adulterant is loaded in the inner crucible of nested type crucible according to any one of claim 1 to 4；
(2) under vacuum described crystal growth raw material is heated to 300～450 DEG C, and is incubated 2～20 hours and carries out pretreatment；
(3) when keeping evacuation, the nested type crucible filling pretreated raw material is cooled to room temperature, the outer crucible of sealing by fusing；And
(4) the nested type crucible after sealing by fusing is inserted crucible degrowth stove, carry out crystal growth by Bridgman-Stockbarger method.
The method of growth strontium iodide crystal the most according to claim 5, it is characterised in that in step (1), the environment of described humidity not higher than 5% is the inert ambient environment that water and oxygen content are all not higher than 1000ppm.
The method of growth strontium iodide crystal the most according to claim 5, it is characterised in that in step (2), described vacuum condition is that vacuum is not higher than 0.1Pa.
The method of growth strontium iodide crystal the most according to claim 7, it is characterised in that described vacuum condition be vacuum be 10-3Below Pa.
The method of growth strontium iodide crystal the most according to claim 5, it is characterised in that use Eu2+、Eu3+、Tl+、Pb2+、Yb2+And Yb3+The iodide of ion, bromide, chloride or fluoride are as adulterant, and doping content is 0～10at%, and optimal doping content is relevant with doping ionic species.
The method of growth strontium iodide crystal the most according to claim 5, it is characterised in that do not use adulterant, the strontium iodide crystal of growth undoped.
The method of 11. growth strontium iodide crystal according to claim 5, it is characterised in that in step (4), described crystal growth comprises the following steps:
At 2～10 hours fusing crystal growth raw materials of 550～700 DEG C of insulations；
Control growth interface thermograde, at 10～60 DEG C/cm, declines crucible with the speed of 0.1～5.0mm/ hour and carries out crystal growth；
Crystal growth terminates rear furnace temperature and reduces by 50～100 DEG C, makes crystal and crucible anneal in position 1～20 hour；And
Room temperature is naturally cooled to after cooling to 100 DEG C with the speed of 10～50 DEG C/h.
The method of 12. growth strontium iodide crystal according to claim 5, it is characterised in that in crystal growth, uses seed crystal to carry out inoculation growth.
The method of 13. growth strontium iodide crystal according to claim 5, it is characterised in that in crystal growth, uses spontaneous nucleation growth.
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| CN108560044A (en) * | 2018-06-01 | 2018-09-21 | 中国科学院理化技术研究所 | For CsB4O6Double-layer crucible for F crystal growth and CsB4O6F crystal growth method |
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| JP2000247778A (en) * | 1999-02-25 | 2000-09-12 | Toshiba Ceramics Co Ltd | Quartz glass crucible, its production and pulling up of silicon single crystal using the same |
| CN201428006Y (en) * | 2009-04-08 | 2010-03-24 | 北京滨松光子技术股份有限公司 | Vacuum quartz crucible used for growth of single crystals by descent method |
| CN101982568A (en) * | 2010-09-27 | 2011-03-02 | 中国计量学院 | Method for growing strontium iodide scintillating crystals by nonvacuum crucible descent method |
| CN102899714A (en) * | 2012-09-25 | 2013-01-30 | 四川大学 | Growth process and growth container of phosphorus-silicon-cadmium single crystal |
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| JP2000247778A (en) * | 1999-02-25 | 2000-09-12 | Toshiba Ceramics Co Ltd | Quartz glass crucible, its production and pulling up of silicon single crystal using the same |
| CN201428006Y (en) * | 2009-04-08 | 2010-03-24 | 北京滨松光子技术股份有限公司 | Vacuum quartz crucible used for growth of single crystals by descent method |
| CN101982568A (en) * | 2010-09-27 | 2011-03-02 | 中国计量学院 | Method for growing strontium iodide scintillating crystals by nonvacuum crucible descent method |
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