CN107675247B - A method of reducing quartz ampoule breakage rate in scintillation single crystal preparation process - Google Patents
A method of reducing quartz ampoule breakage rate in scintillation single crystal preparation process Download PDFInfo
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- C30B11/00—Single-crystal growth by normal freezing or freezing under temperature gradient, e.g. Bridgman-Stockbarger method
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- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/06—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the coating material
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- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/22—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the process of coating
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- C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
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- C30B29/00—Single crystals or homogeneous polycrystalline material with defined structure characterised by the material or by their shape
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Abstract
The present invention discloses a kind of method for reducing quartz ampoule breakage rate in scintillation single crystal preparation process, quartz ampoule is drawn into upper coarse and lower fine special-shaped quartz tube, and in inner wall plated film, outer wall installs foil gauge, by the feedback control crystal growth speed of strain amplitude, prevents quartz ampoule breakage, be inverted special-shaped quartz tube after Crystallization, it is to be cooled to after room temperature, take out scintillation crystal.Advantages of the present invention: it is packed into before crystal raw material in special-shaped quartz inside pipe wall plated film, both it can avoid special-shaped quartz tube and generated the adhesion between crystal, it is kept completely separate conducive to crystal will be generated with special-shaped quartz tube tube body, it can avoid quartz ampoule again and directly squeeze crystal, help to reduce crystalline mi defect, reduce crystal self-absorption probability, reduce crystal cleavage risk, significantly improve scintillator internal performance, in addition, not needing to break quartz ampoule taking-up crystal into pieces after the completion of crystal growth cooling, it need to only be open and pour out crystal, can be recycled after quartz ampoule cleaning.
Description
Technical field
The invention belongs to crystalline material preparation fields, and in particular to quartz ampoule breakage rate in a kind of preparation of reduction scintillation single crystal
Method.
Background technique
Scintillation single crystal material is usually semiconductor material with wide forbidden band.High-energy photon (such as ultraviolet light, X-ray, gamma-rays) enters
When penetrating, more a series of complex reciprocations occur with the lattice of material, including photoelectric effect, Compton scattering and electronics are to effect
It answers, in this process, forms many electron hole pairs in conduction band and valence band and go out and be excited.Subsequent electronics to and hole it is (final
Form exciton) it moves in the material, and captured by the defects of forbidden band.Electrons and holes are captured concurrent in the centre of luminescence
Raw radiation transistion, forms flashing.By scintillation single crystal material can the high-energy photon of sightless, inconvenient measurement,
It is converted into a wavelength range, some strength, the visible light of certain duration, reuses general visible detection device,
Such as photomultiplier tube (PMT), photodiode (PD), charge-coupled device (CCD) are converted into pulse current or voltage letter
Number, using signal processing and conversion circuit, digital signal is converted to, the image viewing and spectrum point of high-energy photon can be realized
Analysis.Scintillation single crystal material is widely used in the X-ray detection X of every profession and trade, in high-energy physics, nuclear medicine, space exploration, geology
Large-scale application has been obtained during the X-ray detection X of exploration etc..And it is answered in national security (safety inspection), industry
There is great development potentiality with (nondestructive inspection, real time monitoring) aspect.
Scintillation single crystal material requirements material purity is high, preferably in vacuum environment generally in 99.99% or more, preparation process
In, avoid oxidation reaction and other pollutions.Preparation process is usually to be first to heat to material melting point or more, heat preservation a period of time, to
It after liquid is stablized, is slowly moved using descent method or czochralski method, general speed is less than 5mm/ hours, has molecule enough
Time by the promotion of free energy, is regularly arranged into the monocrystal of long-range order on generated interface.
Compared with czochralski method, descent method (also known as Bridgman-Stockbarger method) has some advantages: raw material can be sealed in crucible,
Reduce leakage and pollution caused by volatilization, makes the easy control of components of crystal;It is easy to operate that (descent method only needs to move down
Dynamic, czochralski method not only needs to move up and down, while also needing to rotate), it can be with the crystal of growing large-size.The crystal product that can be grown
Kind is also very much, and easily realizes sequencing growth;It, in this way can be one since the melt in each crucible can be individually nucleated
Several crucibles are put into simultaneously in a crystal growing furnace, yield rate and working efficiency can be greatly improved.
The quartz ampoule crucible and platinum crucible that descent method generally uses at present, which have, is easy molding, and sealing is convenient, it is transparent (can
Directly to observe crystal growth condition) etc. advantages, application it is more extensive.However the coefficient of expansion of quartz ampoule is small, at 0~1000 DEG C
Linear expansion coefficient is only 5 × 10 in range-6K-1, volume vary with temperature it is very small, but the scintillator crystal materials coefficient of expansion compared with
It is low, for example sodium iodide (NaI) coefficient of expansion is 47.4 × 10-6K-1, scintillator crystal materials volume varies with temperature bigger.It passes
System quartz ampoule is cylindrical shape, bottom end band tip, due to the difference of the two coefficient of expansion, in scintillation single crystal preparation process,
With the variation of temperature, quartz ampoule is very easy to be split up, once being split up, air can enter in sample from quartz ampoule crack, sample
Once ingress of air will all cancel, so as to cause the complete of whole raw materials, time and the consumption put into preparation process early period
Portion's energy also wastes therewith.Even if quartz ampoule is not split up during the preparation process, there is still a need for break quartz ampoule into pieces after being successfully prepared
Crystal could be taken out, therefore quartz ampoule can only be disposable, this will cause greatly to waste.More seriously, quartz ampoule strikes
After broken, crystal and quartz ampoule adhesion are serious, and crystal by stiction force due to being acted on, and inside cracks and becomes waste product, entirely
The technical issues of it is high that preparation process prepares failure rate, will cause the great wasting of resources.
Summary of the invention
In order to solve the above technical problems, the present invention provides quartz ampoule breakage rate in a kind of reduction scintillation single crystal preparation process
Method.It is packed into before crystal raw material in special-shaped quartz inside pipe wall plated film, cooperates outer wall foil gauge, both can avoid special-shaped quartz tube and life
It at the adhesion between crystal, is kept completely separate conducive to crystal will be generated with special-shaped quartz tube tube body, and can avoid quartz ampoule and directly squeeze
Piezocrystal body helps to reduce crystalline mi defect, reduces crystal self-absorption probability, reduces crystal cleavage risk, significantly improve
Scintillator internal performance, in addition, not needing to break quartz ampoule taking-up crystal into pieces, need to being only open and pour out after the completion of crystal growth cooling
Crystal can be recycled after quartz ampoule cleaning.
Specific technical solution is as follows:
A method of quartz ampoule breakage rate in scintillation single crystal preparation process is reduced, quartz ampoule is drawn into upper coarse and lower fine
Special-shaped quartz tube, and in inner wall plated film, outer wall installs foil gauge, by the feedback control crystal growth speed of strain amplitude, in advance
Anti- quartz ampoule is damaged, is inverted special-shaped quartz tube after Crystallization, takes out scintillation crystal, the specific steps are as follows:
(1) quartzy pipe drawing
No defect is selected, the quartz ampoule of inner wall smooth is dried after being cleaned repeatedly with deionized water, heated using oxyhydrogen flame
To 1900~2000 DEG C, soften quartz ampoule, is drawn into upper coarse and lower fine special-shaped quartz tube;
(2) special-shaped quartz inside pipe wall plated film
It is dried after above-mentioned special-shaped quartz tube is cleaned repeatedly with deionized water, uniformly carries out silicon nitride plated film, shape in inner wall
At silicon nitride plated film special-shaped quartz tube;
(3) special-shaped quartz pipe outer wall installs foil gauge
It is bonded at equal intervals from bottom end to top with refractory ceramics glue in above-mentioned silicon nitride plated film special-shaped quartz pipe outer wall
Three high temperature strain foils, the lead of the high temperature strain foil are connected to external charge amplifier, and charge amplifier is connected to control
Device;
(4) scintillation single crystal is added and prepares raw material
It is uniformly mixed with the raw material of scintillation single crystal according to a certain ratio, raw material is filled in above-mentioned silicon nitride plated film abnormity
In quartz ampoule;
(5) Vacuum Package
Welding bleeding point is heated by oxyhydrogen flame in the top of silicon nitride plated film special-shaped quartz tube after loading raw material, passes through
Vacuum pump will be evacuated inside the special-shaped quartz tube, after special-shaped quartz tube internal vacuum reaches requirement, use hydrogen-oxygen
Flame closes special-shaped quartz tube, and respectively welds a upper fixed ring in top and bottom end;
(6) prepared by scintillation single crystal
Special-shaped quartz tube is moved into single crystal growing furnace, is connected in the fixed link of movement mechanism using top fixed ring, bottom end
The preparatory indwelling wirerope of fixed ring, sets melting zone and crystal region temperature, starts to warm up, and reaches setting value, raw material to temperature
Completely after melting, held for some time sets fall off rate, and under movement mechanism drive, driving special-shaped quartz tube position is opened
Begin to decline, during decline, by controller according to strain amplitude, adjusts crystal growth speed, prevention quartz ampoule is damaged, to sample
After all dropping to crystal region temperature, special-shaped quartz tube position stops decline, held for some time;
(7) scintillation single crystal is separated with special-shaped quartz tube tube body
It keeps special-shaped quartz tube top fixed ring motionless, pulls the wirerope of bottom end fixed ring connection, it slowly will be special-shaped
The scintillation single crystal of quartz ampoule turned upside down, generation is moved to spacious top from narrow bottom end, is always maintained at this position, protects
Temperature starts to cool down according to preset program after a certain period of time, after temperature is reduced to room temperature, takes out special-shaped quartz tube, is cut with glass cutter
Open the thicker top of special-shaped quartz tube, pour out scintillation crystal, be saved in it is spare in vacuum tank, special-shaped quartz tube cleaning, dry after
It is spare to be saved in vacuum tank.
The special-shaped quartz tube upper end 18~20mm of outer diameter, lower end 8~10mm of outer diameter, 1.5~2mm of wall thickness.
The silicon nitride film coating operation is as follows: rf magnetron sputtering coating technique is used, using crystal silicon target as cathode
It is fixed in quartz ampoule, quartzy nozzle is there are the inflating port of argon gas and nitrogen, and vacuum is extracted into 1 × 10 in quartz ampoule-3Pa, by nitrogen argon
The ratio of gas volume ratio 2:1~3:1 adjusts vacuum degree to 3 × 10-1Pa starts to plate silicon nitride film, while uniform rotation quartz
Pipe, is uniformly required with reaching side wall film layer;Every sputtering 5 minutes, suspends 10 minutes, in case quartz ampoule is burst;After sputtering 10 times
It inflates within cooling 30 minutes, takes out quartz ampoule.
The silicon nitride coating film thickness is 0.8~1 μm.
The vacuum degree is 1 × 10-3Pa or less.
The special-shaped quartz tube can be used for preparing the scintillation material and their compound halogen of halide, sulfide base
Compound and mixture scintillation single crystal.
This method have the advantage that:
1, special-shaped quartz tube of the present invention with generally upper coarse and lower fine, bottom end with tip substitutes traditional standard cylindrical body, bottom
The quartz ampoule with tip is held, and on the basis of fixed ring is installed on existing quartz ampoule top, fixed ring is installed in bottom end again, forms top
Respectively there are the structure of a fixed ring in end and bottom end.In crystal preparation process, completed to crystal growth, before not starting cooling, top
Hold fixed ring motionless, pull bottom end fixed ring, be inverted slow quartz ampoule, while under the effect of gravity, inner wall plated film, crystal with
Without adhesion, the crystal of generation is easy to slide into spacious top from narrow bottom end quartz ampoule, carries out cooling operation again later,
Due to, there are a fixed gap, being not in since crystal and quartzy two kinds of material expansion coefficient differences are big between crystal and quartz ampoule
Lead to the phenomenon that quartz ampoule rises brokenly in preparation process.In temperature-fall period, crystal is not contacted with quartz ampoule, not will receive quartz ampoule
It squeezes, internal stress is reduced, and is helped to reduce crystalline mi defect, is reduced crystal self-absorption probability, reduces crystal cleavage wind
Danger, significantly improves scintillator internal performance, production efficiency greatly improved.
2, the present invention is before being packed into crystal raw material, and in special-shaped quartz inside pipe wall plated film, there are two effects for this plated film: first is that can
To avoid special-shaped quartz tube and the adhesion between crystal is generated, cooperates the crystal generated after special-shaped quartz tube turned upside down also from narrow
Narrow bottom end is moved to spacious top, can will more thoroughly generate crystal and be kept completely separate with special-shaped quartz tube tube body;Second is that
Since plated film has certain coefficient of expansion and elasticity, can directly squeeze crystal to avoid quartz ampoule, thus can in special-shaped quartz tube and
Buffer function is played between crystal, and quartz ampoule is avoided to rise brokenly in crystal growing process.
3, make placement foil gauge that quartz ampoule can be monitored in real time by signal amplifier and controller in quartzy pipe outer wall
Strained situation adjust rate of crystalline growth and by strain feedback, make to be applied to the external force of quartz ampoule when crystal growth can
In tolerance range, make the strain of quartz ampoule in controlled range, it is possible to prevente effectively from the generation of quartz ampoule breakage.
4, it after the completion of crystal growth cooling of the present invention, does not need to break quartz ampoule taking-up crystal into pieces, it is only necessary to again with glass cutter
The opening being of moderate size is opened on special-shaped quartz tube top, is poured out crystal, can be recycled, be reduced not after quartz ampoule cleaning
Necessary waste, largely save the cost.
5, since coating temperature is higher than the fusing point of scintillation material, after generation crystal is separated with special-shaped quartz tube tube body, plated film
It stays on quartz ampoule, may be reused.
Detailed description of the invention
Fig. 1 is currently used quartzy tube shape;
Fig. 2 is the special-shaped quartz tube schematic diagram that the present invention uses;
Fig. 3 is arrangement schematic diagram of the quartz ampoule in single crystal growing furnace;
Fig. 4 is the controller flow chart that the present invention uses.
In figure, 1-top fixed ring;2-bleeding points;3-tube bodies;4-tips;5-cutting lines;6-bottom end fixed rings;
7-foil gauges;8-fixed links;9-wirerope;10-foil gauge lines;11-furnace bodies;12-silicon nitride plated films.
Specific embodiment
The present invention is described in detail with reference to the accompanying drawing, but protection scope of the present invention is not limited by embodiment.
Fig. 2 is the special-shaped quartz tube schematic diagram that the present invention uses, and Fig. 3 is arrangement schematic diagram of the quartz ampoule in single crystal growing furnace.
By taking indium-doped (NaI:In) the scintillation single crystal material of sodium iodide as an example:
(1) quartzy pipe drawing
No defect is selected, the quartz ampoule of inner wall smooth is dried after being cleaned repeatedly with deionized water, heated using oxyhydrogen flame
To 1900~2000 DEG C, soften quartz ampoule, is drawn into upper coarse and lower fine special-shaped quartz tube;
(2) special-shaped quartz inside pipe wall plated film
It is dried after above-mentioned special-shaped quartz tube is cleaned repeatedly with deionized water, uniformly carries out silicon nitride plated film 12 in inner wall,
Form silicon nitride plated film special-shaped quartz tube;
(3) special-shaped quartz pipe outer wall installs foil gauge
It is bonded at equal intervals from bottom end to top with refractory ceramics glue in above-mentioned silicon nitride plated film special-shaped quartz pipe outer wall
Three high temperature strain foils 7, the high temperature strain foil 7 are connected to external charge amplifier, charge amplification by foil gauge line 10
Device is connected to controller, and Fig. 4 is the controller flow chart that the present invention uses.
(4) scintillation single crystal is added and prepares raw material
It is uniformly mixed with the raw material of scintillation single crystal according to a certain ratio, raw material is filled in above-mentioned silicon nitride plated film abnormity
In quartz ampoule;
(5) Vacuum Package
Welding bleeding point 2 is heated by oxyhydrogen flame in the top of silicon nitride plated film special-shaped quartz tube after loading raw material, leads to
Crossing vacuum pump will be evacuated inside the special-shaped quartz tube, after special-shaped quartz tube internal vacuum reaches requirement, use hydrogen
Oxygen flame closes special-shaped quartz tube, and welds a top fixed ring 1 on top, welds a bottom end fixed ring 6 in bottom end;
(6) prepared by scintillation single crystal
Special-shaped quartz tube is moved into single crystal growing furnace, is connected in the fixed link 8 of movement mechanism using top fixed ring 1, bottom
The preparatory indwelling wirerope 9 of fixed ring 6 is held, melting zone and crystal region temperature is set, starts to warm up, reach setting value to temperature,
After raw material melts completely, held for some time sets fall off rate, under movement mechanism drive, drives special-shaped quartz tube
Position is begun to decline, and during decline, by controller according to strain amplitude, adjusts crystal growth speed, and prevention quartz ampoule is damaged,
After sample all drops to crystal region temperature, special-shaped quartz tube position stops decline, held for some time;
(7) scintillation single crystal is separated with special-shaped quartz tube tube body
Keep special-shaped quartz tube top fixed ring 1 motionless, the wirerope 9 for pulling bottom end fixed ring 6 to connect slowly will be special-shaped
The scintillation single crystal of quartz ampoule turned upside down, generation is moved to spacious top from narrow bottom end, is always maintained at this position, protects
Temperature starts to cool down according to preset program after a certain period of time, after temperature is reduced to room temperature, takes out special-shaped quartz tube, is existed with glass cutter
It is cut at the thicker top cutting line 5 of special-shaped quartz tube, pours out scintillation crystal, be saved in spare in vacuum tank, special-shaped quartz tube
To be saved in vacuum tank spare after cleaning, drying.
Conventional shape quartz ampoule (A group) is chosen respectively, the present invention does not increase the abnormity of foil gauge using inner wall plated film outer wall
Quartz ampoule (B group), the present invention increase each 10 samples of every group of special-shaped quartz tube (C group) of foil gauge using inner wall plated film outer wall simultaneously
Product carry out scintillation single crystal preparation test, and statistics breakage is as shown in table 1:
1 quartz ampoule breakage contrast table of table
Group | A | B | C |
Sample number | 10 | 10 | 10 |
Damaged number | 5 | 2 | 0 |
Breakage rate | 50% | 20% | 0% |
Seen from table 1, scintillation single crystal preparation is carried out using conventional shape quartz tube shape, breakage rate is high reaches for quartz ampoule
50%, it will cause the significant wastage of resource.It is single that flashing is carried out using the special-shaped quartz tube that inner wall plated film outer wall does not increase foil gauge
Crystalline substance preparation, it is 20% that the breakage rate of quartz ampoule, which significantly reduces,.The special-shaped quartz tube for increasing foil gauge using inner wall plated film outer wall, can
To reach the breakage rate of quartz ampoule for 0, it can be seen that, the present invention has substantive distinguishing features and significant progress.
Claims (6)
1. a kind of method for reducing quartz ampoule breakage rate in scintillation single crystal preparation process, it is characterised in that: quartz ampoule to be drawn into
Upper coarse and lower fine special-shaped quartz tube, and in inner wall plated film, outer wall installs foil gauge, raw by the feedback control monocrystalline of strain amplitude
Long speed, prevention quartz ampoule is damaged, is inverted special-shaped quartz tube after Crystallization, takes out scintillation crystal, the specific steps are as follows:
(1) quartzy pipe drawing
No defect is selected, the quartz ampoule of inner wall smooth is dried after being cleaned repeatedly with deionized water, is heated to using oxyhydrogen flame
1900~2000 DEG C, soften quartz ampoule, is drawn into upper coarse and lower fine special-shaped quartz tube;
(2) special-shaped quartz inside pipe wall plated film
It is dried after above-mentioned special-shaped quartz tube is cleaned repeatedly with deionized water, uniformly carries out silicon nitride plated film in inner wall, form nitrogen
SiClx plated film special-shaped quartz tube;
(3) special-shaped quartz pipe outer wall installs foil gauge
In above-mentioned silicon nitride plated film special-shaped quartz pipe outer wall, from bottom end to top, it is bonded three at equal intervals with refractory ceramics glue
High temperature strain foil, the lead of the high temperature strain foil are connected to external charge amplifier, and charge amplifier is connected to controller;
(4) scintillation single crystal is added and prepares raw material
It is uniformly mixed with the raw material of scintillation single crystal according to a certain ratio, raw material is filled in above-mentioned silicon nitride plated film special-shaped quartz
Guan Zhong;
(5) Vacuum Package
Welding bleeding point is heated by oxyhydrogen flame in the top of silicon nitride plated film special-shaped quartz tube after loading raw material, passes through vacuum
Pump will be evacuated inside the special-shaped quartz tube, after special-shaped quartz tube internal vacuum reaches requirement, be sealed using oxyhydrogen flame
Special-shaped quartz tube is closed, and respectively welds a upper fixed ring in top and bottom end;
(6) prepared by scintillation single crystal
Special-shaped quartz tube is moved into single crystal growing furnace, is connected in the fixed link of movement mechanism using top fixed ring, bottom end is fixed
The preparatory indwelling wirerope of ring, sets melting zone and crystal region temperature, starts to warm up, and reaches setting value to temperature, raw material is complete
After melting, held for some time sets fall off rate, under movement mechanism drive, under driving special-shaped quartz tube position starts
Drop during decline, by controller according to strain amplitude, adjusts crystal growth speed, prevention quartz ampoule is damaged, to sample whole
After dropping to crystal region temperature, special-shaped quartz tube position stops decline, held for some time;
(7) scintillation single crystal is separated with special-shaped quartz tube tube body
It keeps special-shaped quartz tube top fixed ring motionless, the wirerope of bottom end fixed ring connection is pulled, slowly by special-shaped quartz
The scintillation single crystal of pipe turned upside down, generation is moved to spacious top from narrow bottom end, is always maintained at this position, heat preservation one
Start to cool down according to preset program after fixing time, after temperature is reduced to room temperature, take out special-shaped quartz tube, is cut with glass cutter different
The thicker top of shape quartz ampoule, pours out scintillation crystal, be saved in it is spare in vacuum tank, special-shaped quartz tube cleaning, dry after save
It is spare to vacuum tank.
2. reducing the method for quartz ampoule breakage rate in scintillation single crystal preparation process as described in claim 1, it is characterised in that: institute
State special-shaped quartz tube upper end 18~20mm of outer diameter, lower end 8~10mm of outer diameter, 1.5~2mm of wall thickness.
3. reducing the method for quartz ampoule breakage rate in scintillation single crystal preparation process as described in claim 1, which is characterized in that institute
It is as follows to state silicon nitride film coating operation: using rf magnetron sputtering coating technique, being fixed on quartz using crystal silicon target as cathode
In pipe, quartzy nozzle is there are the inflating port of argon gas and nitrogen, and vacuum is extracted into 1 × 10 in quartz ampoule-3Pa, by nitrogen argon gas volume ratio
The ratio of 2:1~3:1 adjusts vacuum degree to 3 × 10-1Pa starts to plate silicon nitride film, while uniform rotation quartz ampoule, to reach side
The requirement of wall even film layer;Every sputtering 5 minutes, suspends 10 minutes, in case quartz ampoule is burst;It fills within cooling 30 minutes after sputtering 10 times
Gas takes out quartz ampoule.
4. reducing the method for quartz ampoule breakage rate in scintillation single crystal preparation process as described in claim 1, it is characterised in that: institute
Stating silicon nitride coating film thickness is 0.8~1 μm.
5. reducing the method for quartz ampoule breakage rate in scintillation single crystal preparation process as described in claim 1, it is characterised in that: institute
Stating vacuum degree is 1 × 10-3Pa or less.
6. reducing the method for quartz ampoule breakage rate in scintillation single crystal preparation process as described in claim 1, it is characterised in that: institute
It states special-shaped quartz tube and is used to prepare halide, the scintillation material of sulfide base and their complex halide and mixture
Scintillation single crystal.
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