CN100552096C - A kind of improved BaY that is applicable to 2F 8The temperature gradient method of single crystal growth and device thereof - Google Patents
A kind of improved BaY that is applicable to 2F 8The temperature gradient method of single crystal growth and device thereof Download PDFInfo
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- CN100552096C CN100552096C CNB2007101511803A CN200710151180A CN100552096C CN 100552096 C CN100552096 C CN 100552096C CN B2007101511803 A CNB2007101511803 A CN B2007101511803A CN 200710151180 A CN200710151180 A CN 200710151180A CN 100552096 C CN100552096 C CN 100552096C
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Abstract
A kind of improved BaY that is applicable to
2F
8The improvement of small-angle crucible that the temperature gradient method of single crystal growth and this method are used and relevant single-crystal growing apparatus.Small-angle crucible provided by the invention is made with high purity graphite, and the shouldering at crucible middle part partly is the taper shape of handstand, and the drift angle of circular cone is 25 °～35 °.This single-crystal growing apparatus comprises an aforesaid small-angle crucible and other improved relative unit.The main improvement of other relative unit is, at the top drilling of molybdenum skin insulated tank, and leave the space that is not less than 2cm between alumina ceramic plate and molybdenum system crucible tray.This improved growth BaY
2F
8The main points of the temperature gradient method of single crystal are: under the axial-temperature gradient that is not less than 6 ℃/mm, 1.8mm/ hour rate of temperature fall is lowered the temperature and growing crystal so that crystalline growth velocity is not higher than.The inventive method also is fit to all kinds of adulterated BaY
2F
8The growth of single crystal.
Description
[technical field]:
The invention belongs to optoelectronic information material technology field, particularly a kind of heavy metal fluoride BaY
2F
8Single crystal and adulterated BaY
2F
8Growth of the temperature gradient method of single crystal and the small-angle crucible that uses thereof and to the improvement of single-crystal growing apparatus.
[background technology]:
The method of growing crystal mainly contains crystal pulling method, falling crucible method, temperature gradient method (among the present invention or abbreviate as warm terraced method), flame melt method, zone melting method and laser pedestal pulling method etc. from melt, wherein crystal pulling method (being called Czoncharlski method again) is used the most extensively, and its originator is J.Czochralski.On the other hand, heavy metal fluoride BaY
2F
8Single crystal is a kind of potential photoelectron material, at present, and the BaY that domestic and foreign literature is reported
2F
8What the growth of single crystal was all adopted is crystal pulling method
[1,2,3,4]Near because the BaY the fusing point
2F
8The melt thickness, mobile poor, convection effects is not obvious, very easily oxidation and the impurity that forms swims in bath surface of fluorochemical when vacuum degree deficiency in addition when causing this kind of Czochralski grown crystal, very easily causes constitutional supercooling, the shouldering difficulty is difficult to grow high quality, large-sized single crystal.In recent years, existing in the domestic literature with the crystal pulling method BaY that grows
2F
8The report of single crystal, but all have problems such as the rate of growing up is low, size is little.From BaY
2F
8Crystalline habit, Czochralski grown are not effective meanss the most.
[summary of the invention]:
The objective of the invention is to solve above shortcomings in the prior art, a kind of improved temperature gradient method growth BaY is provided
2F
8Single crystal and adulterated BaY
2F
8The small-angle crucible that single crystal and this method are used reaches the improvement to relevant crystal growing apparatus.
The present invention uses the small-angle crucible and the single-crystal growing apparatus thereof of particular design, uses a kind of improved temperature gradient method growth BaY
2F
8Single crystal under specific thermograde and rate of temperature fall, utilizes this method can grow the second best in quality BaY
2F
8Single crystal under temperature and the suitable prerequisite of rate of temperature fall, is decided with the volume of crucible raw material big or small and that added on the crystalline volume size principle.
The BaY that is used for provided by the invention
2F
8Single crystal and adulterated BaY
2F
8The bottom of the small-angle crucible of the temperature gradient method growth of single crystal is the seeding capillary channel, and the diameter of capillary channel is 2.5～3.5mm, and its length is greater than 20mm; The shouldering at crucible middle part is the taper shape for standing upside down partly, and the drift angle of circular cone is 25 °～35 °, and the convergence part between shouldering part and the seeding capillary channel is designed to the cambered surface fillet; The length of the equal-diameter part on crucible top is greater than 10mm.
The small-angle crucible adopts high purity graphite to make, to guarantee that in the burner hearth be reducing atmosphere.The top of small-angle crucible installs crucible cover additional, to prevent the volatilization of raw material.
A kind of improved single-crystal growing apparatus that contains above-mentioned small-angle crucible, this single-crystal growing apparatus comprises an aforesaid small-angle crucible and a hollow base made from stainless steel, settle a cyclic alumina ceramic plate on the base, the crucible tray (holder of water-cooled molybdenum) that the burner hearth center is provided with a molybdenum system leaves the space that is not less than 2cm between ring-shaped pottery plate and the aluminium holder.The small-angle crucible places on the holder of water-cooled molybdenum, and small-angle crucible periphery is the heating tungsten bar, and the heating tungsten bar of small-angle crucible and periphery thereof places among the multilayer molybdenum skin insulated tank of top drilling.Axial-temperature gradient in the improved monocrystal growing furnace is not less than 6 ℃/mm.
A kind of improved BaY
2F
8Single crystal thermograde growth method, the step of this method is as follows:
The first, with high-purity BaF
2, YF
3By 1: 2 mole proportioning weighing, grind evenly, drying is placed in the small-angle crucible of aforesaid single-crystal growing apparatus;
The second, the above-mentioned small-angle crucible that raw material is housed is installed in the above-mentioned improved single-crystal growing apparatus (stove).Burner hearth is evacuated to the burner hearth internal gas pressure is lower than 5 * 10
-3Behind the Pa, charge into high-purity argon gas and make protection gas.Heat temperature raising to 1200 ℃, and insulation 2 hours under this temperature;
The 3rd so that crystalline growth velocity is not higher than 1.8mm/ hour rate of temperature fall is lowered the temperature and growing crystal.After estimating that whole raw materials grow up to crystal, about fast cooling to 200 ℃, cut off the electricity supply.When whole growth system cools during to room temperature, close water coolant, open burner hearth, can obtain BaY
2F
8Single crystal.
Advantage of the present invention and beneficial effect:
1, the terraced method growth of small-angle crucible temperature provided by the invention BaY
2F
8The method of single crystal has overcome BaY
2F
8Near crystal raw material thickness, mobile poor thereby should not use the shortcoming of Czochralski grown extremely fusing point relies on measure and condition that the present invention advises, by simple cooling, BaY
2F
8Crystal raw material crystallization automatically is a single crystal, and crystal mass is good, size is big.
2, the inventive method is easy to operate, efficient is high, conservation.Method provided by the invention is easy to automatic control, makes whole growth process become convenient, smooth, efficient, does not have the tailing residue substantially.
3, the present invention not only is fit to BaY
2F
8The growth of single crystal, experimental result show that it also is fit to mix the BaY of impurity (as various rare earth ions)
2F
8The growth of single crystal.
[description of drawings]:
Fig. 1 is the small-angle plumbago crucible structural representation that the inventive method is used;
Fig. 2 is the structural representation of single-crystal growing apparatus in the inventive method;
Fig. 3 is the axial temperature field distribution curve in the improved single crystal growing furnace;
Fig. 4 is to use the Er:BaY of the inventive method growth
2F
8The single crystal photo.
Wherein, 1. temperature-controlling thermal couple; 2. alumina plate; 3. temperature-measuring heat couple; 4. top drilling; 5. be incubated the molybdenum skin; 6. heating tungsten bar; 7. plumbago crucible; 8. bottom perforate; 9. water-cooled molybdenum holder; 10. stainless steel base; About 29 degree of 11 little drift angles; 12. crucible cover; 13. crucible outer wall; 14. shouldering part; 15. connection cambered surface; 16. seeding part.
[embodiment]:
The unique design of embodiment 1, small-angle crucible
The crucible design as shown in Figure 1.The bottom of crucible is the seeding capillary channel, and its diameter is 2mm.The kapillary of this kind yardstick diameter helps the selection of the single direction of growth in the crystalline spontaneous crystallization process, if diameter is too small, the surface tension that is produced will cause melt to be difficult to enter capillary channel.The length of this routine seeding capillary channel is 30mm.The taper shape of the middle part of crucible (shouldering part) for standing upside down, the drift angle that is characterized in circular cone is the Small angle subtended angle, is about 29 °.This is different from other crystal (as CaF
2, crystal such as NaF) warm terraced method growth in the cone angle of shouldering part of used crucible.Relevant Theoretical Calculation shows that the angle of She Ji circular cone drift angle has met BaY herein
2F
8The crystalline crystallization property helps the selection of the single direction of growth in the spontaneous crystallization process, is to obtain good quality crystalline key point.
The shouldering part is designed to the cambered surface fillet with the intercapillary convergence part of seeding, and this kind design makes crystal growth be difficult for undergoing mutation to shouldering by seeding, guarantees the integrity of crystal growth.
The length on the top of crucible (equal-diameter part) is set according to the spatial dimension with constant axial thermograde, is 40mm in this example.
Used crucible is made with high purity graphite, to guarantee that in the burner hearth be reducing atmosphere.
The crucible top is added with crucible cover, to prevent the volatilization of raw material.
Suitable temperature gradient is warm terraced method growth BaY
2F
8One of crystalline key factor.Figure 2 shows that the structural representation of single-crystal growing apparatus in the inventive method.Adopt vacuum tungsten bar resistive heating, crucible is placed in the heating element center, is incubated with multilayer concentric molybdenum skin drum around the heating element.Base is a Stainless Steel Products, and the base top adds puts the ring-type alumina ceramic plate.Leave the space that is not less than 2cm between ring-shaped pottery plate and the crucible tray.
The space is left at the top drilling of molybdenum skin insulated tank and the center of alumina ceramic plate, is one of characteristics of the present invention, its objective is to help forming axial-temperature gradient bigger and longer distance.Fig. 3 is the temperature gradient curve of actual measurement.
1, get the raw materials ready high-purity BaF
2, YF
3By 1: 2 mole proportioning weighing, and the ErF of adding 2mol.%
3, ground and mixed is even in agate mortar, dry for standby.
2, shove charge is the ready raw material small-angle plumbago crucible of packing into.
3, vacuumize and burner hearth is evacuated to the burner hearth internal gas pressure is lower than 5 * 10
-3Behind the Pa, charge into high-purity argon gas and make protection gas.
4, melt heat temperature raising to 1200 ℃, and insulation 2 hours under this temperature melt fully to guarantee raw material, mix.
5, the FP93 automatic temperature control instrument that cooling uses SHIMADEN company to produce is by 4 ℃/hour speed uniform decrease in temperature, to carry out crystal growth.Because thermograde is 8 ℃/mm in the burner hearth of adjusting in advance, the speed of growth of real crystal is 0.5mm/ hour.Wherein, the process of being finished to seeding by the beginning crystallization needs 30 hours approximately.
6, after outage estimates that whole raw materials grow up to crystal, about fast cooling to 200 ℃, cut off the electricity supply.
7, get and brilliant close water coolant when whole growth system cools during to room temperature, open burner hearth, promptly obtain 2mol.%Er:BaY
2F
8Single crystal.
Fig. 4 is for using the Er of the terraced method growth of small-angle temperature
3+: BaY
2F
8The photo of single crystal.
Reference:
[1]L.F.Johnson?and?H.J.Guggenheim.New?Laser?Lines?in?the?Visible?from?Er
3+Ions?inBaY
2F
8[J].Appl.Phys.Lett.，1972，20(12)：474
[2]L.F.Johnson?and?H.J.Guggenheim.Electronic-and?Phonon-Terminated?Laser?Emissionfrom?Ho
3+in?BaY
2F
8.[J].IEEE?Journal?of?Quantum?Electronics，1974，QE-10(4)：442
[3]A.A.Kaminskii，S.E.Sarkisov，F.Below，et?al.Spectroscopic?and?Laser?Properties?ofEr
3+-doped?Monoclinic?BaY
2F
8Single?Crystals[J].Optical?and?Quantum?Electronics，1990，22：95-105
[4]A.Baraldi，R.Cpelletti.Role?of?Er
3+concentration?in?high-resolution?spectra?of?BaY
2F
8singlecrystals.Physical?Review?B?72，2005，075132.
Claims (4)
1, a kind of BaY that is applicable to
2F
8Single crystal and adulterated BaY
2F
8The small-angle crucible of the temperature gradient method growth of single crystal is characterized in that the bottom of this small-angle crucible is the seeding capillary channel, and the diameter of capillary channel is 2.5～3.5mm, and its length is greater than 20mm; The shouldering at crucible middle part is the taper shape for standing upside down partly, and the drift angle of circular cone is 25 °～35 °, and the convergence part between shouldering part and the seeding capillary channel is designed to the cambered surface fillet; The length of the equal-diameter part on crucible top is greater than 10mm.
2, small-angle crucible according to claim 1 is characterized in that, the small-angle crucible adopts high purity graphite to make, to guarantee that in the burner hearth be reducing atmosphere.
3, small-angle crucible according to claim 1 and 2 is characterized in that, the top of small-angle crucible installs crucible cover additional, to prevent the volatilization of raw material.
4, a kind of improved temperature gradient method growth BaY
2F
8Single crystal and adulterated BaY
2F
8The method of single crystal is characterized in that: (1) is used and is contained each described small-angle crucible among the claim 1-3; (2) axial-temperature gradient is not less than 6 ℃/mm in the burner hearth; (3) 1.8mm/ hour rate of temperature fall is lowered the temperature and growing crystal so that crystalline growth velocity is not higher than.
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|---|---|---|---|
| CNB2007101511803A CN100552096C (en) | 2007-12-21 | 2007-12-21 | A kind of improved BaY that is applicable to 2F 8The temperature gradient method of single crystal growth and device thereof |
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|---|---|---|---|
| CNB2007101511803A CN100552096C (en) | 2007-12-21 | 2007-12-21 | A kind of improved BaY that is applicable to 2F 8The temperature gradient method of single crystal growth and device thereof |
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|---|---|
| CN101275272A CN101275272A (en) | 2008-10-01 |
| CN100552096C true CN100552096C (en) | 2009-10-21 |
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| CN104059668A (en) * | 2013-03-21 | 2014-09-24 | 海洋王照明科技股份有限公司 | Terbium/ytterbium double-doped alkaline earth sodium yttrium fluoride up-conversion luminescent material, preparation method and organic light-emitting diode |
| CN104562183B (en) * | 2014-12-31 | 2018-01-19 | 西南技术物理研究所 | Large scale rare-earth adulterates yttrium fluoride barium method for monocrystal growth |
| CN109881158B (en) * | 2019-03-04 | 2020-07-14 | 上海交通大学 | Crucible capable of reducing material splashing in electron beam evaporation process and manufacturing method thereof |
| CN114075696A (en) * | 2021-11-04 | 2022-02-22 | 安徽光智科技有限公司 | Growth method of zinc selenide crystal |
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Non-Patent Citations (4)
| Title |
|---|
| New Laser Lines in the Visible from Er3+ Ions in BaY2F8. L F Johnson等.Appl. Phys. Lett.,Vol.20 No.12. 1972 |
| New Laser Lines in the Visible from Er3+ Ions in BaY2F8. L F Johnson等.Appl. Phys. Lett.,Vol.20 No.12. 1972 * |
| Spectroscopic and Laser Properties of Er3+-dopedMonoclinic BaY2F8 Single Crystal. A A Kaminskii等.Optical and Quantum Electronics,Vol.22 . 1990 |
| Spectroscopic and Laser Properties of Er3+-dopedMonoclinic BaY2F8 Single Crystal. A A Kaminskii等.Optical and Quantum Electronics,Vol.22 . 1990 * |
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