CN107675247A - A kind of method for reducing quartz ampoule breakage rate in scintillation single crystal preparation process - Google Patents

A kind of method for reducing quartz ampoule breakage rate in scintillation single crystal preparation process Download PDF

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CN107675247A
CN107675247A CN201710932518.2A CN201710932518A CN107675247A CN 107675247 A CN107675247 A CN 107675247A CN 201710932518 A CN201710932518 A CN 201710932518A CN 107675247 A CN107675247 A CN 107675247A
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special
crystal
quartz ampoule
quartz tube
shaped quartz
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CN107675247B (en
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祁阳
谭俊
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Northeastern University China
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Northeastern University China
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    • C—CHEMISTRY; METALLURGY
    • C30—CRYSTAL GROWTH
    • 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
    • C30B11/00—Single-crystal growth by normal freezing or freezing under temperature gradient, e.g. Bridgman-Stockbarger method
    • C30B11/002—Crucibles or containers for supporting the melt
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/0021—Reactive sputtering or evaporation
    • C23C14/0036—Reactive sputtering
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • 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
    • C23C14/0641—Nitrides
    • C23C14/0652—Silicon nitride
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • 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
    • C23C14/34—Sputtering
    • C23C14/35—Sputtering by application of a magnetic field, e.g. magnetron sputtering
    • C—CHEMISTRY; METALLURGY
    • C30—CRYSTAL GROWTH
    • 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
    • C30B11/00—Single-crystal growth by normal freezing or freezing under temperature gradient, e.g. Bridgman-Stockbarger method
    • C30B11/006—Controlling or regulating
    • C—CHEMISTRY; METALLURGY
    • C30—CRYSTAL GROWTH
    • 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
    • C30B29/00—Single crystals or homogeneous polycrystalline material with defined structure characterised by the material or by their shape
    • C30B29/10—Inorganic compounds or compositions
    • C30B29/12—Halides
    • C—CHEMISTRY; METALLURGY
    • C30—CRYSTAL GROWTH
    • 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
    • C30B29/00—Single crystals or homogeneous polycrystalline material with defined structure characterised by the material or by their shape
    • C30B29/10—Inorganic compounds or compositions
    • C30B29/46—Sulfur-, selenium- or tellurium-containing compounds

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  • Chemical Kinetics & Catalysis (AREA)
  • Mechanical Engineering (AREA)
  • Inorganic Chemistry (AREA)
  • Crystals, And After-Treatments Of Crystals (AREA)

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 inwall plated film, outer wall installs foil gauge, by the feedback control crystal growth speed of strain amplitude, prevention quartz ampoule is damaged, is 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：Load before crystal raw material in special-shaped quartz inside pipe wall plated film, both special-shaped quartz tube can have been avoided and generated the adhesion between crystal, it is kept completely separate beneficial to by generation crystal with special-shaped quartz tube body, quartz ampoule can be avoided directly to extrude crystal again, help to reduce crystalline mi defect, reduce crystal self-absorption probability, reduce crystal cleavage risk, significantly improve scintillator internal performance, in addition, after the completion of crystal growth cooling, it is not necessary to break quartz ampoule into pieces and take out crystal, it need to only be open and pour out crystal, can be recycled after quartz ampoule cleaning.

Description

A kind of method for reducing quartz ampoule breakage rate in scintillation single crystal preparation process
Technical field
The invention belongs to crystalline material preparation field, and in particular to one kind reduces quartz ampoule breakage rate in prepared by scintillation single crystal Method.
Background technology
Scintillation single crystal material is typically semiconductor material with wide forbidden band.High-energy photon (such as ultraviolet, X ray, gamma-rays) enters When penetrating, more a series of complex reciprocations, including photoelectric effect, Compton scattering and electronics occur to effect with the lattice of material Should, in this process, many electron hole pairs are formed in conduction band and valence band and goes out and is excited.Subsequent electronics pair and hole are (final Form exciton) move in the material, and captured by the defects of forbidden band.Electronics and hole 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, A wavelength range, some strength, the visible ray of certain duration are converted into, reuses general visible detection device, Such as photomultiplier (PMT), photodiode (PD), charge coupling device (CCD), it is converted into pulse current or voltage letter Number, using signal transacting and change-over circuit, be converted to data signal, you can realize the image viewing and spectrum point of high-energy photon 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 answered in national security (safety inspection), industry There is great development potentiality with (nondestructive inspection, in real time monitoring) aspect.
Scintillation single crystal material requirements material purity is high, typically more than 99.99%, preferably in vacuum environment in preparation process In, avoid oxidation reaction and other pollutions.Preparation process is usually to be first to heat to more than material melting point, insulation a period of time, is treated After liquid is stable, 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 the interface generated.
Compared with czochralski method, descent method (also known as Bridgman-Stockbarger method) has some advantages：Raw material can be sealed in crucible, Leakage and pollution caused by reducing volatilization, make the easy control of components of crystal；It is simple to operate that (descent method only needs to move down Dynamic, czochralski method not only needs to move up and down, while also needs to rotate), can be with the crystal of growing large-size.The crystal product that can be grown Kind is also a lot, and easily realizes that sequencing grows；, so can be one because the melt in each crucible can be individually nucleated Several crucibles are put into simultaneously in individual crystal growing furnace, yield rate and operating efficiency can be greatly improved.
The quartz ampoule crucible and platinum crucible that descent method typically uses at present have easily shaping, and sealing is convenient, it is transparent (can Directly to observe crystal growth condition) etc. advantage, application it is more extensive.But the coefficient of expansion of quartz ampoule is small, at 0~1000 DEG C In the range of linear expansion coefficient be only 5 × 10-6K-1, its 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.Pass System quartz ampoule is cylindrical shape, bottom band tip, due to the difference of the two coefficient of expansion, in scintillation single crystal preparation process, With the change 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, complete so as to the whole raw materials, time and the consumption that cause to put into preparation process early stage Portion's energy also wastes therewith.Even if quartz ampoule is not split up in preparation process, there is still a need for breaking 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 turns into waste product, entirely Preparation process prepares that mortality is high, can cause the technical problem of the great wasting of resources.
The content 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.In special-shaped quartz inside pipe wall plated film before loading crystal raw material, coordinate outer wall foil gauge, can both avoid special-shaped quartz tube and life Into the adhesion between crystal, it is kept completely separate beneficial to by generation crystal with special-shaped quartz tube body, quartz ampoule can be avoided directly to squeeze again Piezocrystal body, help to reduce crystalline mi defect, reduce crystal self-absorption probability, reduce crystal cleavage risk, significantly improve Scintillator internal performance, in addition, after the completion of crystal growth cooling, it is not necessary to break quartz ampoule into pieces and take out crystal, need to only be open and pour out Crystal, it can be recycled after quartz ampoule cleaning.
Concrete technical scheme is as follows：
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 inwall plated film, outer wall installation 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, comprises the following steps that：
(1) quartzy pipe drawing
No defect is selected, the quartz ampoule of inner wall smooth, dries after being cleaned repeatedly with deionized water, is heated using oxyhydrogen flame To 1900~2000 DEG C, soften quartz ampoule, be drawn into upper coarse and lower fine special-shaped quartz tube；
(2) special-shaped quartz inside pipe wall plated film
Dried after above-mentioned special-shaped quartz tube is cleaned repeatedly with deionized water, silicon nitride plated film, shape are uniformly carried out in inwall Into silicon nitride plated film special-shaped quartz tube；
(3) special-shaped quartz pipe outer wall installation foil gauge
In above-mentioned silicon nitride plated film special-shaped quartz pipe outer wall, from bottom to top, it is bonded at equal intervals with refractory ceramics glue 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 preparing raw material is added
The raw material of scintillation single crystal is uniformly mixed with according to a certain ratio, and raw material is filled in above-mentioned silicon nitride plated film abnormity In quartz ampoule；
(5) Vacuum Package
Welding bleeding point is heated in the top of silicon nitride plated film special-shaped quartz tube after raw material is loaded by oxyhydrogen flame, passes through Vavuum 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 a retainer ring is respectively welded in top and bottom；
(6) prepared by scintillation single crystal
Special-shaped quartz tube is moved into single crystal growing furnace, is connected to using top retainer ring in the fix bar of motion, bottom The advance indwelling steel wire rope of retainer ring, sets melting zone and crystal region temperature, starts to warm up, and treats that temperature reaches setting value, raw material Completely after melting, held for some time, fall off rate is set, under motion drive, driving special-shaped quartz tube position is opened Begin to decline, during decline, by controller according to strain amplitude, adjust crystal growth speed, prevention quartz ampoule is damaged, treats sample After all dropping to crystal region temperature, special-shaped quartz tube position stops declining, held for some time；
(7) scintillation single crystal separates with special-shaped quartz tube body
Keep special-shaped quartz tube top retainer ring motionless, the steel wire rope of bottom retainer ring connection is pulled, slowly by abnormity Quartz ampoule turned upside down, the scintillation single crystal of generation are moved to the top of spaciousness from narrow bottom, are always maintained at this position, protect Start to cool according to preset program after warm certain time, after temperature is reduced to room temperature, takes out special-shaped quartz tube, cut with glass cutter Open the thicker top of special-shaped quartz tube, pour out scintillation crystal, be saved in it is standby in vacuum tank, special-shaped quartz tube cleaning, dry after It is standby to be saved in vacuum tank.
The special-shaped quartz tube upper end 18~20mm of external diameter, lower end 8~10mm of external diameter, 1.5~2mm of wall thickness.
The silicon nitride film coating operation is as follows：Using rf magnetron sputtering coating technique, using crystal silicon target as negative pole It is fixed in quartz ampoule, the quartzy mouth of pipe leaves the inflation inlet of argon gas and nitrogen, and vacuum is extracted into 1 × 10 in quartz ampoule-3Pa, by nitrogen argon Gas volume is than 2:1~3:1 ratio, regulation vacuum to 3 × 10-1Pa starts to plate silicon nitride film, while uniform rotation quartz Pipe, is uniformly required with reaching side wall film layer；Often sputter 5 minutes, suspend 10 minutes, in case quartz ampoule is burst；After sputtering 10 times Cooling is inflated for 30 minutes, takes out quartz ampoule.
The silicon nitride coating film thickness is 0.8~1 μm.
The vacuum is 1 × 10-3Below Pa.
The special-shaped quartz tube can be used for preparing halide, the scintillation material of sulfide base, and their compound halogen Compound and mixture scintillation single crystal.
This method have the advantage that：
1st, the present invention substitutes traditional standard cylinder, bottom with special-shaped quartz tube of the generally upper coarse and lower fine, bottom with tip The quartz ampoule with tip is held, and on the basis of existing quartz ampoule top installation retainer ring, retainer ring is installed in bottom again, forms top Respectively there is the structure of a retainer ring end and bottom.In crystal preparation process, treat that crystal growth is completed, before not starting cooling, top Hold retainer ring motionless, pull bottom retainer ring, be inverted slow quartz ampoule, while under gravity, inwall plated film, crystal with Quartz ampoule is easy to slide into the top of spaciousness from narrow bottom, carries out cooling operation again afterwards without adhesion, the crystal of generation, Be not in because crystal and quartzy two kinds of material expand difference of coefficients are big due to a fixed gap between crystal and quartz ampoule be present Cause the phenomenon that quartz ampoule rises brokenly in preparation process.In temperature-fall period, crystal does not contact with quartz ampoule, will not be by quartz ampoule Extruding, its internal stress are reduced, and are helped to reduce crystalline mi defect, are reduced crystal self-absorption probability, reduce crystal cleavage wind Danger, significantly improves scintillator internal performance, production efficiency greatly improved.
2nd, the present invention is before crystal raw material is loaded, and in special-shaped quartz inside pipe wall plated film, this plated film has two effects：First, can To avoid special-shaped quartz tube and generate the adhesion between crystal, coordinate the crystal generated after special-shaped quartz tube turned upside down also from narrow Narrow bottom is moved to the top of spaciousness, more thoroughly can be kept completely separate generation crystal with special-shaped quartz tube body；Second, Because plated film has certain coefficient of expansion and elasticity, quartz ampoule can be avoided directly to extrude crystal, thus can in special-shaped quartz tube and Cushioning effect is played between crystal, avoids quartz ampoule from rising brokenly in crystal growing process.
3rd, make placement foil gauge in quartzy pipe outer wall, by signal amplifier and controller, quartz ampoule can be monitored in real time Strained situation, and fed back by straining, adjust rate of crystalline growth, make to be applied to the external force of quartz ampoule during crystal growth can In tolerance range, make the strain of quartz ampoule in controlled range, it is possible to prevente effectively from the generation that quartz ampoule is damaged.
4th, after the completion of crystal growth cooling of the present invention, it is not necessary to break quartz ampoule into pieces and take out crystal, it is only necessary to glass cutter again An 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, it is largely cost-effective.
5th, because coating temperature is higher than the fusing point of scintillation material, after generation crystal separates with special-shaped quartz tube body, plated film Stay on quartz ampoule, may be reused.
Brief description of the drawings
Fig. 1 is the quartzy tube shape used at present；
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 retainer ring；2-bleeding point；3-body；4-tip；5-line of cut；6-bottom retainer ring； 7-foil gauge；8-fix bar；9-steel wire rope；10-foil gauge line；11-body of heater；12-silicon nitride plated film.
Embodiment
The present invention is described in detail below in conjunction with the accompanying drawings, 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.
With the indium-doped (NaI of sodium iodide：In) exemplified by scintillation single crystal material：
(1) quartzy pipe drawing
No defect is selected, the quartz ampoule of inner wall smooth, dries after being cleaned repeatedly with deionized water, is heated using oxyhydrogen flame To 1900~2000 DEG C, soften quartz ampoule, be drawn into upper coarse and lower fine special-shaped quartz tube；
(2) special-shaped quartz inside pipe wall plated film
Dried after above-mentioned special-shaped quartz tube is cleaned repeatedly with deionized water, silicon nitride plated film 12 uniformly carried out in inwall, Form silicon nitride plated film special-shaped quartz tube；
(3) special-shaped quartz pipe outer wall installation foil gauge
In above-mentioned silicon nitride plated film special-shaped quartz pipe outer wall, from bottom to top, it is bonded at equal intervals with refractory ceramics glue Three high temperature strain foils 7, the high temperature strain foil 7 are connected to external charge amplifier, electric 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 preparing raw material is added
The raw material of scintillation single crystal is uniformly mixed with according to a certain ratio, and raw material is filled in above-mentioned silicon nitride plated film abnormity In quartz ampoule；
(5) Vacuum Package
Welding bleeding point 2 is heated in the top of silicon nitride plated film special-shaped quartz tube after raw material is loaded by oxyhydrogen flame, leads to Crossing vavuum 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 retainer ring 1 on top, and a bottom retainer ring 6 is welded in bottom；
(6) prepared by scintillation single crystal
Special-shaped quartz tube is moved into single crystal growing furnace, is connected to using top retainer ring 1 in the fix bar 8 of motion, bottom The advance indwelling steel wire rope 9 of retainer ring 6 is held, melting zone and crystal region temperature is set, starts to warm up, treat that temperature reaches setting value, After raw material melting completely, held for some time, fall off rate is set, under motion drive, drive 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 declining, held for some time；
(7) scintillation single crystal separates with special-shaped quartz tube body
Keep special-shaped quartz tube top retainer ring 1 motionless, the steel wire rope 9 for pulling bottom retainer ring 6 to connect, slowly by abnormity Quartz ampoule turned upside down, the scintillation single crystal of generation are moved to the top of spaciousness from narrow bottom, are always maintained at this position, protect Start to cool according to preset program after warm certain time, after temperature is reduced to room temperature, takes out special-shaped quartz tube, existed with glass cutter Cut at the thicker top line of cut 5 of special-shaped quartz tube, pour out scintillation crystal, be saved in standby in vacuum tank, special-shaped quartz tube Clean, dry after to be saved in vacuum tank standby.
Conventional shape quartz ampoule (A groups) is chosen respectively, the present invention does not increase the abnormity of foil gauge using inwall plated film outer wall Quartz ampoule (B groups), the present invention are simultaneously using each 10 samples of every group of special-shaped quartz tube (C groups) of inwall plated film outer wall increase foil gauge Product, carry out scintillation single crystal and prepare experiment, statistics breakage is as shown in table 1：
The quartz ampoule breakage contrast table of table 1
Group A B C
Sample number 10 10 10
Damaged number 5 2 0
Breakage rate 50% 20% 0%
From table 1, scintillation single crystal preparation is carried out using conventional shape quartz tube shape, the breakage rate of quartz ampoule is up to 50%, the significant wastage of resource can be caused.The special-shaped quartz tube for not increasing foil gauge using inwall plated film outer wall enters line flicker list Prepared by crystalline substance, the breakage rate of quartz ampoule is significantly reduced as 20%., can using the special-shaped quartz tube of inwall plated film outer wall increase foil gauge To reach the breakage rate of quartz ampoule as 0, it can be seen that, the present invention has substantive distinguishing features and significant progress.

Claims (6)

  1. A kind of 1. method for reducing quartz ampoule breakage rate in scintillation single crystal preparation process, it is characterised in that：Quartz ampoule is drawn into Upper coarse and lower fine special-shaped quartz tube, and foil gauge is installed in inwall plated film, outer wall, the feedback control monocrystalline for passing through strain amplitude is given birth to Long speed, prevention quartz ampoule is damaged, is inverted special-shaped quartz tube after Crystallization, takes out scintillation crystal, comprises the following steps that：
    (1) quartzy pipe drawing
    No defect is selected, the quartz ampoule of inner wall smooth, dries after being cleaned repeatedly with deionized water, is heated to using oxyhydrogen flame 1900~2000 DEG C, soften quartz ampoule, be drawn into upper coarse and lower fine special-shaped quartz tube；
    (2) special-shaped quartz inside pipe wall plated film
    Dried after above-mentioned special-shaped quartz tube is cleaned repeatedly with deionized water, uniformly carry out silicon nitride plated film in inwall, form nitrogen SiClx plated film special-shaped quartz tube；
    (3) special-shaped quartz pipe outer wall installation foil gauge
    In above-mentioned silicon nitride plated film special-shaped quartz pipe outer wall, from bottom to top, three are bonded 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 preparing raw material is added
    The raw material of scintillation single crystal is uniformly mixed with according to a certain ratio, and raw material is filled in above-mentioned silicon nitride plated film special-shaped quartz Guan Zhong；
    (5) Vacuum Package
    Welding bleeding point is heated in the top of silicon nitride plated film special-shaped quartz tube after raw material is loaded by oxyhydrogen flame, 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 a retainer ring is respectively welded in top and bottom；
    (6) prepared by scintillation single crystal
    Special-shaped quartz tube is moved into single crystal growing furnace, is connected to using top retainer ring in the fix bar of motion, bottom is fixed The advance indwelling steel wire rope of ring, sets melting zone and crystal region temperature, starts to warm up, and treats that temperature reaches setting value, raw material is complete After melting, held for some time, fall off rate is set, under motion drive, under driving special-shaped quartz tube position starts Drop, during decline, by controller according to strain amplitude, crystal growth speed is adjusted, prevention quartz ampoule is damaged, treats sample whole After dropping to crystal region temperature, special-shaped quartz tube position stops declining, held for some time；
    (7) scintillation single crystal separates with special-shaped quartz tube body
    Keep special-shaped quartz tube top retainer ring motionless, the steel wire rope of bottom retainer ring connection is pulled, slowly by special-shaped quartz Pipe turned upside down, the scintillation single crystal of generation are moved to the top of spaciousness from narrow bottom, are always maintained at this position, insulation one Start to cool according to preset program after fixing time, after temperature is reduced to room temperature, take out special-shaped quartz tube, cut with glass cutter different The thicker top of shape quartz ampoule, pours out scintillation crystal, be saved in it is standby in vacuum tank, special-shaped quartz tube cleaning, dry after preserve It is standby to vacuum tank.
  2. 2. the method for quartz ampoule breakage rate in scintillation single crystal preparation process is reduced as claimed in claim 1, it is characterised in that：Institute State special-shaped quartz tube upper end 18~20mm of external diameter, lower end 8~10mm of external diameter, 1.5~2mm of wall thickness.
  3. 3. the method for quartz ampoule breakage rate in scintillation single crystal preparation process is reduced as claimed in claim 1, it is characterised in that institute It is as follows to state silicon nitride film coating operation：Using rf magnetron sputtering coating technique, quartz is fixed on using crystal silicon target as negative pole In pipe, the quartzy mouth of pipe leaves the inflation inlet of argon gas and nitrogen, and vacuum is extracted into 1 × 10 in quartz ampoule-3Pa, by nitrogen argon gas volume ratio 2:1~3:1 ratio, regulation vacuum 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；Often sputter 5 minutes, suspend 10 minutes, in case quartz ampoule is burst；Cool down 30 minutes and fill after sputtering 10 times Gas, take out quartz ampoule.
  4. 4. the method for quartz ampoule breakage rate in scintillation single crystal preparation process is reduced as claimed in claim 1, it is characterised in that：Institute Silicon nitride coating film thickness is stated as 0.8~1 μm.
  5. 5. the method for quartz ampoule breakage rate in scintillation single crystal preparation process is reduced as claimed in claim 1, it is characterised in that：Institute Vacuum is stated as 1 × 10-3Below Pa.
  6. 6. the method for quartz ampoule breakage rate in scintillation single crystal preparation process is reduced as claimed in claim 1, it is characterised in that：Institute Special-shaped quartz tube is stated to can be used for preparing halide, the scintillation material of sulfide base, and their complex halide and mixing Thing scintillation single crystal.
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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN114406218A (en) * 2022-01-23 2022-04-29 宁波磁性材料应用技术创新中心有限公司 Quartz nozzle and preparation method thereof

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101356130A (en) * 2005-10-19 2009-01-28 莫门蒂夫性能材料股份有限公司 Quartz glass crucible and method for treating surface of quartz glass crucible

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101356130A (en) * 2005-10-19 2009-01-28 莫门蒂夫性能材料股份有限公司 Quartz glass crucible and method for treating surface of quartz glass crucible

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN114406218A (en) * 2022-01-23 2022-04-29 宁波磁性材料应用技术创新中心有限公司 Quartz nozzle and preparation method thereof
CN114406218B (en) * 2022-01-23 2023-10-03 宁波磁性材料应用技术创新中心有限公司 Quartz nozzle and preparation method thereof

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