CN102877116B - Closed single crystal growth furnace for crystal growth by molten salt method - Google Patents
Closed single crystal growth furnace for crystal growth by molten salt method Download PDFInfo
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- CN102877116B CN102877116B CN201110195895.5A CN201110195895A CN102877116B CN 102877116 B CN102877116 B CN 102877116B CN 201110195895 A CN201110195895 A CN 201110195895A CN 102877116 B CN102877116 B CN 102877116B
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- 239000013078 crystal Substances 0.000 title claims abstract description 125
- 238000000034 method Methods 0.000 title abstract description 11
- 150000003839 salts Chemical class 0.000 title abstract description 11
- 229910001220 stainless steel Inorganic materials 0.000 claims abstract description 96
- 239000010935 stainless steel Substances 0.000 claims abstract description 96
- 239000011449 brick Substances 0.000 claims abstract description 39
- 239000000919 ceramic Substances 0.000 claims abstract description 35
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 22
- 239000011553 magnetic fluid Substances 0.000 claims abstract description 21
- 229920000742 Cotton Polymers 0.000 claims abstract description 11
- 238000009413 insulation Methods 0.000 claims description 29
- 230000000740 bleeding effect Effects 0.000 claims description 13
- 230000009970 fire resistant effect Effects 0.000 claims description 10
- 238000010438 heat treatment Methods 0.000 claims description 7
- 239000002826 coolant Substances 0.000 claims description 5
- 239000000203 mixture Substances 0.000 claims description 5
- PXXKQOPKNFECSZ-UHFFFAOYSA-N platinum rhodium Chemical compound [Rh].[Pt] PXXKQOPKNFECSZ-UHFFFAOYSA-N 0.000 claims description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 5
- 238000007789 sealing Methods 0.000 claims description 4
- 239000000377 silicon dioxide Substances 0.000 claims description 4
- 229910018487 Ni—Cr Inorganic materials 0.000 claims description 3
- VNNRSPGTAMTISX-UHFFFAOYSA-N chromium nickel Chemical compound [Cr].[Ni] VNNRSPGTAMTISX-UHFFFAOYSA-N 0.000 claims description 3
- 238000003032 molecular docking Methods 0.000 claims description 3
- 230000002093 peripheral effect Effects 0.000 claims description 2
- 230000002459 sustained effect Effects 0.000 claims description 2
- 239000012535 impurity Substances 0.000 abstract description 10
- 230000003287 optical effect Effects 0.000 abstract description 8
- 238000010521 absorption reaction Methods 0.000 abstract description 4
- 239000000498 cooling water Substances 0.000 abstract 1
- 230000000149 penetrating effect Effects 0.000 abstract 1
- 238000002211 ultraviolet spectrum Methods 0.000 abstract 1
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 20
- 238000010792 warming Methods 0.000 description 12
- 229910052697 platinum Inorganic materials 0.000 description 10
- 239000002994 raw material Substances 0.000 description 9
- 238000001228 spectrum Methods 0.000 description 9
- 230000010748 Photoabsorption Effects 0.000 description 7
- 239000007788 liquid Substances 0.000 description 7
- 238000003756 stirring Methods 0.000 description 7
- 238000001816 cooling Methods 0.000 description 6
- 239000000243 solution Substances 0.000 description 6
- 238000010586 diagram Methods 0.000 description 4
- 230000004907 flux Effects 0.000 description 4
- 230000006835 compression Effects 0.000 description 3
- 238000007906 compression Methods 0.000 description 3
- 150000002500 ions Chemical class 0.000 description 3
- 238000002844 melting Methods 0.000 description 3
- 230000008018 melting Effects 0.000 description 3
- 239000004570 mortar (masonry) Substances 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 2
- 238000005336 cracking Methods 0.000 description 2
- 229910016036 BaF 2 Inorganic materials 0.000 description 1
- BTBUEUYNUDRHOZ-UHFFFAOYSA-N Borate Chemical compound [O-]B([O-])[O-] BTBUEUYNUDRHOZ-UHFFFAOYSA-N 0.000 description 1
- 230000003749 cleanliness Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000007716 flux method Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229910052573 porcelain Inorganic materials 0.000 description 1
- 239000012266 salt solution Substances 0.000 description 1
- 238000010583 slow cooling Methods 0.000 description 1
- 230000003595 spectral effect Effects 0.000 description 1
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Abstract
The sealed single crystal growth furnace for the crystal growth by the molten salt method comprises: a ceramic sleeve type hearth wound with a resistance wire; a closed barrel-shaped hollow double-layer stainless steel outer furnace shell positioned outside the hearth; refractory insulating brick/cotton arranged between the furnace shell and the hearth; a thermocouple penetrating through the furnace shell and extending to the outer wall of the hearth; a fireproof insulating brick cover covering the upper port of the hearth; a first vertical central through hole and an observation hole are formed in the center and two sides of the furnace cover; cooling water which circularly flows is filled in the furnace shell; the wall of the furnace shell is provided with an air exhaust port and an air inlet port; a second vertical central through hole and a quartz glass window which are opposite to the first vertical central through hole are arranged in the center of the furnace shell cover; filling atmosphere in the furnace shell; the magnetic fluid is arranged above the furnace shell and is connected with the furnace shell by a corrugated pipe; the seed crystal rod penetrates through the magnetic fluid to be connected with the universal joint and is fixed on the crystal rotating head through the universal joint; the crystal can grow in atmosphere, reduce impurity entering the crystal, improve optical property of the crystal, remove extrinsic absorption generated by the crystal in an ultraviolet spectrum region, and improve the output power of the crystal ultraviolet laser.
Description
Technical field
The invention belongs to the monocrystal growing furnace of field of crystal growth, particularly the airtight monocrystal growing furnace of a kind of crystal growth from f lux.
Technical background
Molten-salt growth method is a kind of common growing method, and the method refers to the method for at high temperature growing crystal in molten salt solution, mainly comprises top-seeded solution growth, seed crystal kyropoulos etc.The method adopts porcelain bushing as burner hearth usually, and outside is around resistance wire as type of heating, and burner hearth is placed in a stainless steel furnace shell, and bottom pad insulating brick, fills fire resistant heat preserving cotton around burner hearth.Crucible is placed on inside burner hearth, can increase and decrease pad according to growth needs, regulates crucible in the position of vertical direction.Furnace mouth adds two blocks of insulating bricks, keeps the thermograde that burner hearth is inner suitable.Insulating brick central punch, ensure that seed rod can pass through, respectively there is an aperture both sides, for observing crystal growth.Seed rod is connected by brilliant rotary head, can rotate according to the speed of setting.Precise control of temperature is realized by S type platinum rhodium thermocouple.This growth furnace temperature range is between a few Baidu to 1200 DEG C, and the too high meeting of growth temperature causes resistance wire to blow.There is in burner hearth larger constant temperature vitellarium, be applicable to some crystal adopting flux method to grow of growth, as borate nonlinear optical crystal β-BaB
2o
4(BBO), LiB
3o
5(LBO), CsLiB
6o
10(CLBO), K
2al
2b
2o
7(KABO), BaAlBO
3f
2(BABF), YAl
3(BO
3)
4(YAB) etc., large-sized transparent single crystal can be grown.
But, find that this crystalloid all exists optical absorption in various degree between 200-300nm during the crystal such as growth KABO, BABF, thus have impact on the ultraviolet frequency double optical output power of crystal.Investigator studies and finds that the extrinsic photoabsorption of this kind of ultraviolet produces because some impurity enters lattice, attempt (as: adopting the measure of high pure raw material, high level of cleanliness) by all means and thoroughly remove impurity, but be difficult to avoid entering of impurity completely.If the growth atmosphere in burner hearth can be changed, by chemical reaction, change foreign ion radius size, thus indirectly control the amount of impurities entering lattice, just can reach the object improving optical property.Current common flux growth stove described above carries out crystal growth under atmospheric environment, cannot change growth atmosphere, thus cannot realize this purpose.
Use crystal growing furnace of the present invention, both the feature of common fused salt crystal growing furnace had been maintained, growth atmosphere can be changed again, even if when using purity not high (analytical pure) raw material, still can effectively control impurity and enter crystal, effectively can solve the extrinsic absorption of ultraviolet that crystal produces due to impurity.
Summary of the invention
The object of this invention is to provide the airtight monocrystal growing furnace of a kind of crystal growth from f lux, can growth atmosphere have been changed.The present invention combines the feature of common molten salt furnace and lifting furnace, has both met the little temperature ladder required for crystal growth from f lux, can change growth atmosphere again, thus effectively controls some impurity and enter lattice, improves some optical property of crystal.
Realize technical scheme of the present invention as follows:
The airtight monocrystal growing furnace of crystal growth from f lux provided by the invention, it comprises:
Ceramic jacket tubular type burner hearth 1;
Be surrounded on the resistance wire as heating source around described ceramic jacket tubular type burner hearth 1;
Be positioned at described ceramic jacket tubular type burner hearth 1 peripheral and described ceramic jacket tubular type burner hearth 1 is surrounded its outer furnace shell 3 of stainless steel;
Pad is loaded on the outer insulating brick between furnace shell 3 inner bottom part and described ceramic jacket tubular type burner hearth 1 of described stainless steel;
Load in the outer fire resistant heat preserving between furnace shell 3 and described ceramic jacket tubular type burner hearth 1 outer wall of described stainless steel cotton;
The thermopair 7 of described ceramic jacket tubular type burner hearth 1 outer wall is extended through outer furnace shell 3 outer wall of described stainless steel;
Be placed on the fireproof insulation brick bell 2 of described ceramic jacket tubular type burner hearth 1 upper port and the cotton upper end of fire resistant heat preserving; The the first vertical central through hole penetrated for seed rod is provided with in the middle of described fireproof insulation brick bell 2; Described first vertical central through hole both sides are respectively equipped with crystal growth vision slit; It is characterized in that,
The outer furnace shell 3 of described stainless steel be the outer furnace shell of airtight barrel-shaped hollow double-layer stainless steel, and described airtight barrel-shaped hollow double-layer stainless steel is outward at the bottom of the bucket wall of furnace shell, bucket and be provided with the airtight runner be connected in bung; Its airtight runner is built with the water coolant circulated;
The furnace wall of the outer furnace shell 3 of described stainless steel is provided with the bleeding point 4 led within the outer furnace shell 3 of described stainless steel and the inlet mouth 5 led within described ceramic jacket tubular type burner hearth 1; Described bleeding point 4 is connected with vacuum mechanical pump by pipeline; Described inlet mouth 5 is connected with atmosphere gas source of the gas;
The bung center of the outer furnace shell 3 of described stainless steel is provided with the second vertical central through hole relative with the first vertical central through hole on described fireproof insulation brick bell 2; The both sides of described second vertical central through hole are respectively equipped with the silica glass window 8 relative with described crystal growth vision slit;
Atmosphere gas gas is full of in the outer furnace shell 3 of described stainless steel;
Be located at the magnetic fluid 6 above the outer furnace shell 3 of described stainless steel, between described magnetic fluid 6 with the bung of the outer furnace shell 3 of described stainless steel, adopt corrugated tube to be connected; Seed rod lower end arrives above crucible through the first vertical central through hole on the second vertical central through hole of the outer furnace shell 3 of magnetic fluid 6, corrugated tube and stainless steel and insulating brick bell 2 successively; Seed rod upper end is connected with universal knot through magnetic fluid 6, is fixed in brilliant rotary head by universal knot.
Described ceramic jacket tubular type burner hearth 1 is highly 300-500mm, and internal diameter is at 80mm-150mm.
Described fireproof insulation brick bell 2 is that two pieces of fireproof insulation brick docking form; Distance between described fireproof insulation brick bell 2 upper surface and outer furnace shell 3 bung of described stainless steel is at 80-200mm.
The internal diameter of the outer furnace shell 3 of described stainless steel is 300-700mm, and height is at 400-800mm.
Described silica glass window 8 diameter is 60-100mm.
A non-airtight stainless steel furnace shell 9 is set with outside described fire resistant heat preserving cotton; Space layer is provided with between described non-airtight stainless steel furnace shell 9 and outer furnace shell 3 inwall of described stainless steel; Filling atmosphere gas gas in described stainless steel outer furnace shell 3 inner chamber, non-airtight stainless steel furnace shell 9 and ceramic jacket tubular type burner hearth 1.
Described thermopair 7 is overlap the S type platinum rhodium thermocouple or K type armoured thermocouple that have silica tube to carry out sealing; The negative pole of described K type armoured thermocouple is nisiloy, the just very nickel chromium triangle of described K type armoured thermocouple.
In the outer furnace shell 3 of described stainless steel, vacuum tightness reaches 10
-6pa, after filling atmosphere gas gas, outer furnace shell 3 internal pressure of stainless steel is within (0 < P <, 2 standard atmospheric pressures) scope.
It is O that described atmosphere encloses source of the gas
2, N
2, Ar, H
2, N
2with H
2gas mixture or Ar and H
2gas mixture.
Described bleeding point 4 and inlet mouth 5 lay respectively at below outer furnace shell 3 side of stainless steel and top, above and below or be on the different positions of sustained height.
When using the airtight monocrystal growing furnace growing crystal of crystal growth from f lux of the present invention, concrete steps are: first the raw material of growing crystal and solubility promoter are mixed according to a certain ratio, in retort furnace, be fused to platinum crucible in batches, then stir, solution is mixed; After cooling, platinum crucible is placed in position suitable in the ceramic jacket tubular type burner hearth 1 of airtight monocrystal growing furnace of the present invention; The fireproof insulation brick bell 2 be positioned on ceramic jacket tubular type burner hearth 1 port is docked by two pieces of fireproof insulation bricks and forms, and the center has the first vertical central through hole penetrated for seed rod; Described first vertical central through hole both sides are respectively equipped with crystal growth vision slit; Seed rod is equipped with one end of seed crystal successively through magnetic fluid 6, corrugated tube, first vertical central through hole of the second vertical central through hole and fireproof insulation brick bell 2 arrives above crucible, and the seed rod the other end (upper end) is connected with universal knot, is fixed in brilliant rotary head; Close inlet mouth 5, open mechanical pump, more slowly open bleeding point 4, vacuumize, bleed complete, first close vacuum valve, then close off-gas pump, open inlet mouth 5, slowly inject required atmosphere gas gas; On this basis, arrange heating schedule, slow raised temperature makes Melt molten, is then cooled near temperature of saturation, moves seed rod by corrugated tube, and make seed crystal contact liquid level, slow cooling carries out crystal growth; After growth terminates, setting program slow cooling, to room temperature, then opens inlet mouth 5, injects air, makes the pressure in the outer furnace shell 3 of stainless steel return to normal pressure, then opens the bell of the outer furnace shell 3 of stainless steel, take out crystal.
The airtight monocrystal growing furnace of crystal growth from f lux of the present invention can be used for the crystal growth of top-seeded solution growth or middle part seed-grain method, crystal growing process is that those skilled in the art understood, use said apparatus can prepare various functional crystal material, these all do not exceed the spirit and scope of the present invention.
Use the airtight monocrystal growing furnace growing crystal of crystal growth from f lux of the present invention, its effect shows: because this crystal growth from f lux is an airtight crystal growing furnace with airtight monocrystal growing furnace, the atmosphere of growth system can be changed, broken the restriction that common crystal growth from f lux can only carry out in air atmosphere; By injecting extraordinary atmosphere gas gas, at high temperature atmosphere gas gas and foreign ion generation chemical reaction, can change foreign ion radius, controls impurity and enter lattice, reach removal impurity, improve the object of some optical property of crystal; With the airtight monocrystal growing furnace growing crystal of crystal growth from f lux of the present invention, effectively can remove the extrinsic absorption of ultraviolet of some non-linear optic crystals, some other optical property is all improved.
Accompanying drawing explanation
Fig. 1 is the structural representation of the present invention's (specific embodiment);
Fig. 2 is the structural representation of the present invention's (another specific embodiment);
Fig. 3 is the UV-permeable spectrum comparison diagram adopting the airtight monocrystal growing furnace of crystal growth from f lux of the present invention and common Flux Growth Furnace growth KABO crystal;
Fig. 4 is the UV-permeable spectrum comparison diagram adopting the airtight monocrystal growing furnace of crystal growth from f lux of the present invention and common Flux Growth Furnace growth YAB crystal;
Specific implementation method:
Below in conjunction with drawings and Examples, the present invention will be further described, and these embodiments, only for illustration of the present invention, are not limited to this.
Embodiment 1:
The airtight monocrystal growing furnace of crystal growth from f lux of the present embodiment, as shown in Figure 1, it comprises: ceramic jacket tubular type burner hearth 1, its internal diameter is 100mm (80mm-150mm), be highly 300mm (300-500mm), and directly fill fire resistant heat preserving cotton between the outer furnace shell 3 of stainless steel; Outer furnace shell 3 internal diameter 350mm (300-700mm) of stainless steel, high 450mm (400-800mm); The airtight barrel-shaped hollow double-layer stainless steel furnace shell outward that the outer furnace shell 3 of this stainless steel makes for double layer hollow stainless steel, at the bottom of its barrel of wall, bucket and be provided with the airtight runner be connected in bung; Its airtight runner is built with the water coolant circulated; Bleeding point 4 is positioned at above outer furnace shell 3 sidewall of stainless steel, and inlet mouth 5 is positioned at below outer furnace shell 3 sidewall of stainless steel; Thermopair 7 is the S type platinum rhodium thermocouple that outer surface cover silica tube carries out sealing; Dock by two pieces the fireproof insulation brick bell 2 formed above ceramic jacket tubular type burner hearth 1, bell center is provided with first vertical central through hole Φ=12mm (between 10-20mm), and respectively there is a crystal growth vision slit both sides of the first vertical central through hole; Fireproof insulation brick bell 2 is 90mm (80-200mm) apart from the bung distance of the outer furnace shell 3 of stainless steel; Stainless steel is outer adopts corrugated tube to be connected between furnace shell 3 with magnetic fluid 6, can move up and down seed rod, be convenient to adjustable range; The bung center of the outer furnace shell 3 of stainless steel is provided with the second vertical central through hole relative with the vertical central through hole of first on fireproof insulation brick bell 2; The both sides of this second vertical central through hole are respectively equipped with the silica glass window 8 (diameter 80mm) relative with described crystal growth vision slit, by silica glass window 8 and described crystal growth vision slit, can observe the growing state of seed crystal.
Adopt the device described in embodiment 1, top-seeded solution growth growth K
2al
2b
2o
7(KABO) crystal.
Take 207g high-purity (99.99%) K
2cO
3, 152g high-purity (99.99%) Al
2o
3, 204g high-purity (99.99%) H
3bO
3107g high-purity (99.99%) NaF, in agate mortar, abundant ground and mixed is even, get part and be placed in platinum crucible (Φ 80 × Φ 90), 500 DEG C are slowly warming up in retort furnace, constant temperature a few hours make gas fully discharge, and then are slowly warming up to 900 DEG C, make melting sources.Through feeding in raw material several times, raw material is all fused in crucible.First platinum crucible puts into common fused salt crystal growing furnace, is warming up to 900 DEG C, stirs 24h with platinum agitator arm.After stirring complete cooling, be placed on by crucible in ceramic jacket tubular type burner hearth 1, furnace mouth adds two pieces of fireproof insulation brick bells 2.Seed rod one end arrives above crucible through the first vertical central through hole on the second vertical central through hole of the outer furnace shell 3 of magnetic fluid 6, corrugated tube and stainless steel and insulating brick bell 2; The seed rod the other end is connected with universal knot through magnetic fluid 6, is fixed on brilliant rotary head by universal knot.
Install, close inlet mouth 5, open mechanical pump, more slowly open bleeding point 4, vacuumize, bleed empty complete, first close vacuum valve, then close off-gas pump.Then open inlet mouth 5, slowly inject desired gas (N
2gas), make pressure in the outer furnace shell 3 of stainless steel reach 0.5 standard atmospheric pressure.Arrange heating schedule, 20h is warming up to 900 DEG C, and along with temperature raises, outer furnace shell 3 internal pressure of stainless steel also increases slightly, finally remains on 0.55 standard atmospheric pressure.Keep 24h under high temperature, be then cooled near temperature of saturation with 10 DEG C/h, to be declined seed rod by bellows compression, make seed crystal contact liquid level, by observing crystal whether melt-off determination temperature of saturation.Higher than temperature of saturation about 5 DEG C, make seed crystal contact liquid level, part melt back, is then cooled to temperature of saturation, starts crystal growth with the rate of temperature fall of 0.1-0.2 DEG C/day, and seed rod rotating speed is 15-20rpm, and positive and negative alternate rotates.Grow after 50 days, obtain KABO crystal and be of a size of 40 × 22 × 12mm
3, crystal is transparent, without cracking.UV-permeable spectrum display crystal does not have extrinsic photoabsorption in 200-300nm region.
And use the KABO crystal that above-mentioned same parameter and condition grow at common molten salt furnace, though growth morphology is without obviously difference, there is serious photoabsorption at ultraviolet band in the crystal of growth; The transmitance comparison diagram of KABO crystal as shown in Figure 3, crystal thickness consistent (d=3mm), a be the crystal grown in common growth furnace through spectrum, b be the crystal grown in airtight monocrystal growing furnace of the present invention through spectrum.
Embodiment 2:
The airtight monocrystal growing furnace of crystal growth from f lux of the present embodiment, as shown in Figure 1, it comprises: ceramic jacket tubular type burner hearth 1 internal diameter is 110mm (80mm-150mm), be highly 350mm (300-500mm), and directly fill fire resistant heat preserving cotton between the outer furnace shell 3 of stainless steel; Outer furnace shell 3 internal diameter 400mm (300-700mm) of stainless steel, high 500mm (400-800mm), the outer furnace shell 3 of stainless steel be the airtight barrel-shaped hollow double-layer stainless steel furnace shell outward made by double layer hollow stainless steel, at the bottom of its barrel of wall, bucket and be provided with the airtight runner be connected in bung; Its airtight runner is built with the water coolant circulated; Bleeding point 4 is positioned at above outer furnace shell 3 sidewall of stainless steel, and inlet mouth 5 is positioned at below outer furnace shell 3 sidewall of stainless steel.Thermopair 7 is the S type platinum rhodium thermocouple that outer surface cover silica tube carries out sealing; Dock by two pieces the fireproof insulation brick bell 2 formed above burner hearth, the first vertical central through hole (between Φ=15mm, 10-20mm) is established in centre, and respectively there is a crystal growth vision slit both sides; Fireproof insulation brick bell 2 is 95mm (80-200mm) apart from the bung distance of the outer furnace shell 3 of stainless steel; Stainless steel is outer to be connected with corrugated tube between furnace shell 3 with magnetic fluid 6, can move up and down seed rod, be convenient to adjustable range.The bung center of the outer furnace shell 3 of stainless steel is provided with the second vertical central through hole relative with the vertical central through hole of first on fireproof insulation brick bell 2; The both sides of this second vertical central through hole are respectively equipped with the silica glass window 8 (diameter 80mm) relative with described crystal growth vision slit, by silica glass window 8 and described crystal growth vision slit, can observe the growing state of seed crystal.
Adopt the device described in embodiment 2, top-seeded solution growth growth YAl
3(BO
3)
4(YAB) crystal.
Take 28g high-purity (99.99%) Y
2o
3, 118g high-purity (99.99%) Al
2o
3, 430g high-purity (99.99%) H
3bO
3, 80g high-purity (99.99%) Li
2cO
3, in agate mortar, abundant ground and mixed is even, and get part and be placed in platinum crucible (Φ 70 × Φ 90), in retort furnace, be slowly warming up to 500 DEG C, constant temperature a few hours make gas fully discharge, and then are slowly warming up to 1200 DEG C, make melting sources.Through feeding in raw material several times, raw material is all fused in crucible.First platinum crucible puts into common fused salt crystal growing furnace, is warming up to 1150 DEG C, stirs 24h with platinum agitator arm.After stirring complete cooling, be placed on by crucible in ceramic jacket tubular type burner hearth 1, the upper port of ceramic jacket tubular type burner hearth 1 adds the fireproof insulation brick bell 2 of two pieces of docking compositions.Seed rod one end arrives above crucible through the first vertical central through hole on the second vertical central through hole of the outer furnace shell 3 of magnetic fluid 6, corrugated tube and stainless steel and fireproof insulation brick bell 2 successively; The seed rod the other end is connected with universal knot through magnetic fluid 6, is fixed on brilliant rotary head by universal knot.
Install, close inlet mouth 5, open mechanical pump, more slowly open bleeding point 4, vacuumize, bleed complete, first close vacuum valve, then close off-gas pump.Place several hours, pressure increases slowly, then remains unchanged, and illustrates that in the outer furnace shell 3 of stainless steel, stopping property is good.Then open inlet mouth 5, slowly inject desired gas (Ar+H2 mixed gas), make pressure in the outer furnace shell 3 of stainless steel reach 0.6 standard atmospheric pressure.Arrange heating schedule, 24h is warming up to 1150 DEG C, and along with temperature raises, pressure also increases slightly, finally remains on 0.7 standard atmospheric pressure.Keep 24h under high temperature, be then cooled near temperature of saturation with 10 DEG C/h, to be declined seed rod by bellows compression, make seed crystal contact liquid level, by observing crystal whether melt-off determination temperature of saturation.Higher than temperature of saturation about 5 DEG C, make seed crystal contact liquid level, part melt back, is then cooled to temperature of saturation, starts with the cooling of the speed of 0.1-0.2 DEG C/d, and be then increased to the speed cooling of 1-2 DEG C/d, carry out crystal growth, seed rod rotating speed is 15-20rpm.Grow after 60 days, obtain YAB crystal and be of a size of 30 × 30 × 25mm
3, heavy 46g, crystal major part areas transparent, without cracking.UV-permeable spectrum display crystal does not have extrinsic photoabsorption in 200-300nm region.
And at the YAB crystal that common molten salt furnace grows, growth morphology is without obvious difference, but there is serious photoabsorption at ultraviolet band in the YAB crystal of common molten salt furnace growth.The transmitance comparison diagram of YAB crystal as shown in Figure 4, crystal thickness consistent (d=2.5mm), a be the crystal grown in common flux growth stove through spectrum, b be the crystal grown in airtight monocrystal growing furnace of the present invention through spectrum.
Embodiment 3:
The airtight growth furnace for growing molten-salt growth method monocrystalline of the present embodiment, as shown in Figure 2, it comprises: ceramic jacket tubular type burner hearth 1 internal diameter is 120mm (80mm-150mm), be highly 380mm (300-500mm), outside fire resistant heat preserving cotton, be set with a non-airtight stainless steel furnace shell 9; Space layer is provided with between this non-airtight stainless steel furnace shell 9 and outer furnace shell 3 inwall of stainless steel; Filling atmosphere gas gas in described stainless steel outer furnace shell 3 inner chamber, non-airtight stainless steel furnace shell 9 and ceramic jacket tubular type burner hearth 1; Place fireproof insulation brick bell 2 above ceramic jacket tubular type burner hearth 1, centre is provided with the first vertical central through hole (between Φ=16mm, 10-20mm), and respectively there is a crystal growth vision slit its both sides; Outer furnace shell 3 internal diameter 450mm (300-700mm) of stainless steel, high 550mm (400-800mm), the outer furnace shell 3 of stainless steel be the airtight barrel-shaped hollow double-layer stainless steel furnace shell outward made by double layer hollow stainless steel, at the bottom of its barrel of wall, bucket and be provided with the airtight runner be connected in bung; Its airtight runner is built with the water coolant circulated; ; Bleeding point 4 is positioned at below outer furnace shell 3 sidewall of stainless steel, and inlet mouth 5 is positioned at above outer furnace shell 3 sidewall of stainless steel; Thermopair 7 is K type armoured thermocouple, and its negative pole is nisiloy, just very nickel chromium triangle; Fireproof insulation brick bell 2 is 100mm (80-200mm) apart from the bung distance of the outer furnace shell 3 of stainless steel; Stainless steel is outer to be connected with corrugated tube between furnace shell 3 with magnetic fluid 6, can move up and down seed rod, be convenient to adjustable range; Stainless steel is outer to be connected with corrugated tube between furnace shell 3 with magnetic fluid 6, can move up and down seed rod, be convenient to adjustable range.The bung center of the outer furnace shell 3 of stainless steel is provided with the second vertical central through hole relative with the vertical central through hole of first on fireproof insulation brick bell 2; The both sides of this second vertical central through hole are respectively equipped with the silica glass window 8 (diameter 80mm) relative with described crystal growth vision slit, by silica glass window 8 and described crystal growth vision slit, can observe the growing state of seed crystal.
Adopt the device described in embodiment 3, top-seeded solution growth growth BABF crystal.
Take 175g high-purity (99.99%) BaF
2, 51g high-purity (99.99%) Al
2o
3, 35g high-purity (99.99%) H
3bO
342g high-purity (99.99%) NaF, in agate mortar, abundant ground and mixed is even, get part and be placed in platinum crucible (Φ 80 × Φ 80), 500 DEG C are slowly warming up in retort furnace, constant temperature a few hours make gas fully discharge, and then are slowly warming up to 950 DEG C, make melting sources.Through feeding in raw material several times, raw material is all fused in crucible.First platinum crucible puts into common fused salt crystal growing furnace, is warming up to 950 DEG C, stirs 24h.After stirring complete cooling, be placed on by crucible in ceramic jacket tubular type burner hearth 1, furnace mouth adds two pieces of fireproof insulation brick bells 2.Seed rod one end arrives above crucible through the first vertical central through hole on the second vertical central through hole of the outer furnace shell 3 of magnetic fluid 6, corrugated tube and stainless steel and insulating brick bell 2; The seed rod the other end is connected with universal knot through magnetic fluid 6, is fixed on brilliant rotary head by universal knot.
Install, close inlet mouth 5, open mechanical pump, more slowly open bleeding point 4, vacuumize, bleed complete, first close vacuum valve, then close off-gas pump.Open inlet mouth 5, then slowly inject desired gas (N
2+ H
2mixed gas), make pressure in the outer furnace shell 3 of stainless steel be 1.1 standard atmospheric pressures.Arrange heating schedule, 20h is warming up to 950 DEG C, and along with temperature raises, pressure also increases slightly, finally remains on 115 standard atmospheric pressures.Keep 20h under high temperature, make to mix, be then cooled near temperature of saturation with 10 DEG C/h, to be declined seed rod by bellows compression, make seed crystal contact liquid level, by observing crystal whether melt-off determination temperature of saturation.Higher than temperature of saturation about 5 DEG C, seed crystal is made to contact liquid level, part melt back, then be cooled to temperature of saturation, start crystal growth with 0.1-0.2 DEG C/d rate of temperature fall, seed rod rotating speed is 15-20rpm, after growth in 45 days, obtain BABF crystal and be of a size of 15 × 10 × 20mm
3, crystal is transparent, and without inclusion, UV-permeable spectrum display crystal does not have extrinsic photoabsorption in 200-300nm region.
And at the BABF crystal that common molten salt furnace grows, growth morphology is without obvious difference, but there is serious photoabsorption at ultraviolet band in crystal; Fig. 3 and 4 is similar to through spectral class.
Claims (10)
1. the airtight monocrystal growing furnace of crystal growth from f lux, it comprises:
Ceramic jacket tubular type burner hearth (1);
Be surrounded on described ceramic jacket tubular type burner hearth (1) resistance wire as heating source around;
Be positioned at described ceramic jacket tubular type burner hearth (1) peripheral and described ceramic jacket tubular type burner hearth (1) is surrounded its outer furnace shell (3) of stainless steel;
Pad is loaded on the outer insulating brick between furnace shell (3) inner bottom part and described ceramic jacket tubular type burner hearth (1) of described stainless steel;
Load in the outer fire resistant heat preserving between furnace shell (3) and described ceramic jacket tubular type burner hearth (1) outer wall of described stainless steel cotton; The thermopair (7) of described ceramic jacket tubular type burner hearth (1) outer wall is extended through outer furnace shell (3) outer wall of described stainless steel;
Be placed on the fireproof insulation brick bell (2) of described ceramic jacket tubular type burner hearth (1) upper port and the cotton upper end of fire resistant heat preserving; The the first vertical central through hole penetrated for seed rod is provided with in the middle of described fireproof insulation brick bell (2); Described first vertical central through hole both sides are respectively equipped with crystal growth vision slit; It is characterized in that,
The outer furnace shell (3) of described stainless steel is the outer furnace shell of airtight barrel-shaped hollow double-layer stainless steel, at the bottom of the bucket wall of the outer furnace shell of described airtight barrel-shaped hollow double-layer stainless steel, bucket and be provided with the airtight runner be connected in bung; Its airtight runner is built with the water coolant circulated;
The furnace wall of the outer furnace shell (3) of described stainless steel is provided with the bleeding point (4) leading to outer furnace shell (3) inner chamber of described stainless steel and the inlet mouth (5) led within described ceramic jacket tubular type burner hearth (1); Described bleeding point (4) is connected with vacuum mechanical pump by pipeline; Described inlet mouth (5) is connected with atmosphere gas source of the gas;
The bung center of the outer furnace shell (3) of described stainless steel is provided with the second vertical central through hole relative with the first vertical central through hole on described fireproof insulation brick bell (2); The both sides of the second vertical central through hole of the bung of the outer furnace shell (3) of described stainless steel are respectively equipped with the silica glass window (8) relative with described crystal growth vision slit;
Atmosphere gas gas is full of in the outer furnace shell (3) of described stainless steel;
Be located at the magnetic fluid (6) of outer furnace shell (3) top of described stainless steel, between described magnetic fluid (6) with the bung of the outer furnace shell (3) of described stainless steel, adopt corrugated tube to be connected; Through magnetic fluid, (the first vertical central through hole on the second vertical central through hole of the outer furnace shell (3) of 6) ﹑ corrugated tubes and stainless steel and fireproof insulation brick bell (2) arrives above crucible successively in seed rod lower end; Seed rod upper end is connected with universal knot through magnetic fluid (6), is fixed in brilliant rotary head by universal knot.
2., by the airtight monocrystal growing furnace of crystal growth from f lux according to claim 1, it is characterized in that, described ceramic jacket tubular type burner hearth (1) is highly 300-500mm, and internal diameter is at 80mm-150mm.
3. by the airtight monocrystal growing furnace of crystal growth from f lux according to claim 1, it is characterized in that, described fireproof insulation brick bell (2) is that two pieces of fireproof insulation brick docking form; Distance between described fireproof insulation brick bell (2) upper surface and outer furnace shell (3) bung of described stainless steel is at 80-200mm.
4. by the airtight monocrystal growing furnace of crystal growth from f lux according to claim 1, it is characterized in that, the internal diameter of the outer furnace shell (3) of described stainless steel is 300-700mm, and height is at 400-800mm.
5., by the airtight monocrystal growing furnace of crystal growth from f lux according to claim 1, it is characterized in that, silica glass window (8) diameter is 60-100mm.
6. by the airtight monocrystal growing furnace of crystal growth from f lux according to claim 1, it is characterized in that, outside described fire resistant heat preserving cotton, be set with a non-airtight stainless steel furnace shell (9); Space layer is provided with between described non-airtight stainless steel furnace shell (9) and outer furnace shell (3) inwall of described stainless steel; Outer furnace shell (3) inner chamber of described stainless steel, non-airtight stainless steel furnace shell (9) and ceramic jacket tubular type burner hearth (1) interior filling atmosphere gas gas.
7. by the airtight monocrystal growing furnace of crystal growth from f lux according to claim 1, it is characterized in that, described thermopair (7) is overlap the S type platinum rhodium thermocouple or K type armoured thermocouple that have silica tube to carry out sealing; The negative pole of described K type armoured thermocouple is nisiloy, the just very nickel chromium triangle of described K type armoured thermocouple.
8. by the airtight monocrystal growing furnace of crystal growth from f lux according to claim 1, it is characterized in that, outer furnace shell (3) the interior vacuum tightness of described stainless steel reaches 10
-6pa, after filling atmosphere gas gas, outer furnace shell (3) internal pressure of stainless steel is being greater than 0 to being less than within the scope of 2 standard atmospheric pressures.
9., by the airtight monocrystal growing furnace of crystal growth from f lux according to claim 1, it is characterized in that, described atmosphere gas source of the gas is O
2, N
2, Ar, H
2, N
2with H
2gas mixture or Ar and H
2gas mixture.
10. by the airtight monocrystal growing furnace of crystal growth from f lux according to claim 1, it is characterized in that, described bleeding point (4) and inlet mouth (5) lay respectively at below outer furnace shell (3) side of stainless steel and top, above and below or be on the different positions of sustained height.
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| CN106283175B (en) * | 2016-09-22 | 2018-08-24 | 中国科学院理化技术研究所 | growing nonlinear optical crystal L iB3O5、CsB3O5and Cs L iB6O10Method (2) |
| CN107557861B (en) * | 2017-10-21 | 2019-05-10 | 福州大学 | A kind of growing method and its process units suitable for BPOC monocrystalline |
| CN109870402A (en) * | 2019-03-04 | 2019-06-11 | 西南交通大学 | A kind of liquid alkali metal Dynamic Corrosion experimental provision |
| CN114214721A (en) * | 2019-08-21 | 2022-03-22 | 眉山博雅新材料股份有限公司 | Open type temperature field |
| EP3954810A4 (en) * | 2020-06-05 | 2022-05-04 | Meishan Boya Advanced Materials Co., Ltd. | High-uniformity crystal growth method and apparatus without annealing |
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| CN2559657Y (en) * | 2002-08-27 | 2003-07-09 | 中国科学院福建物质结构研究所 | Double controlling temperature crystal grower furnace |
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| US7306673B2 (en) * | 2004-08-20 | 2007-12-11 | Corning Incorporated | Furnace purification and metal fluoride crystal grown in a purified furnace |
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| CN2559657Y (en) * | 2002-08-27 | 2003-07-09 | 中国科学院福建物质结构研究所 | Double controlling temperature crystal grower furnace |
| CN101384756A (en) * | 2006-03-01 | 2009-03-11 | 三菱瓦斯化学株式会社 | Process for producing zno single crystal according to method of liquid phase growth |
| CN101787560A (en) * | 2009-01-23 | 2010-07-28 | 中国科学院理化技术研究所 | Special-shaped crucible for adjusting gas-liquid temperature difference of crystal grown by melt pulling method |
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