CN102877116A - Closed monocrystalline growth furnace for molten salt method crystal growth - Google Patents
Closed monocrystalline growth furnace for molten salt method crystal growth Download PDFInfo
- Publication number
- CN102877116A CN102877116A CN2011101958955A CN201110195895A CN102877116A CN 102877116 A CN102877116 A CN 102877116A CN 2011101958955 A CN2011101958955 A CN 2011101958955A CN 201110195895 A CN201110195895 A CN 201110195895A CN 102877116 A CN102877116 A CN 102877116A
- Authority
- CN
- China
- Prior art keywords
- furnace shell
- stainless steel
- airtight
- hole
- growth
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Images
Landscapes
- Crystals, And After-Treatments Of Crystals (AREA)
Abstract
A closed monocrystalline growth furnace for the molten salt method crystal growth comprises a ceramic bushing hearth wound with a resistance wire, a closed barrel-shaped hollow double-layer stainless steel outer furnace shell positioned outside the hearth, fireproof heat-insulation bricks/cotton arranged between the furnace shell and the hearth, a thermocouple traversing the furnace shell and extending to the outer wall of the hearth, and a fireproof heat-insulation brick furnace cover covering the upper port of the hearth, wherein the center and two sides of the furnace cover are provided with a first vertical central through hole and observation holes respectively; cooling water which flows in a circulating manner is contained in the furnace shell; the wall of the furnace shell is provided with an aspirating hole and an air inlet; the center of the cover of the furnace shell is provided with a second vertical central through hole opposite to the first vertical central through hole, and quartz glass windows; an atmospheric gas is filled to the inside of the furnace shell; a magnetofluid is arranged over the furnace shell and is connected with the furnace shell through a bellow; and a seed crystal rod traverses the magnetofluid, is connected with a universal knot, and is fixed on a crystal rotation head through the universal knot. The furnace enables crystals to grow under the atmospheric gas, the entry of impurities into the crystals to be reduced, the optical properties of the crystals to be improved, the extrinsic absorption generated by the crystals in an ultraviolet spectrum region to be removed, and the ultraviolet laser output power to be improved.
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 molten-salt growth method crystal growth.
Technical background
Molten-salt growth method is a kind of common growing method, and the method refers to the at high temperature method of 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 the outer surrounding resistance wire is as type of heating, and burner hearth is placed in the stainless steel furnace shell, fills the fire resistant heat preserving cotton around the bottom pad insulating brick, burner hearth.Crucible is placed on the burner hearth the inside, 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 inner suitable thermograde of burner hearth.The insulating brick central punch guarantees that seed rod can pass through, and respectively there is an aperture both sides, is used for observing the crystal growth.Seed rod connects by brilliant rotary head, can be according to the speed rotation of setting.Realize accurately control temperature by S type platinum rhodium thermocouple.This growth furnace temperature range is between several Baidu to 1200 ℃, and the too high meeting of growth temperature causes resistance wire to blow.Have larger constant temperature vitellarium in the burner hearth, some adopt the crystal of flux method growth to be fit to growth, such as borate non-linear optic 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., can grow large-sized transparent single crystal.
Yet, find that all there is optical absorption in various degree in this crystalloid between 200-300nm during the crystal such as growth KABO, BABF, thereby affected the ultraviolet frequency double optical output power of crystal.The investigator studies and finds that the extrinsic photoabsorption of this class ultraviolet produces owing to some impurity enters lattice, attempt (as: adopting high pure raw material, the highly measure of cleaning) by all means and thoroughly remove impurity, but be difficult to avoid fully entering of impurity.If can change the growth atmosphere in the burner hearth, by chemical reaction, change the foreign ion radius size, thereby indirectly control enters the amount of impurities of lattice, just can reach the purpose of improving optical property.Common flux growth stove described above is to carry out the crystal growth under atmospheric environment at present, can't change growth atmosphere, thereby can't realize this purpose.
Use crystal growing furnace of the present invention, the characteristics that both kept common fused salt crystal growing furnace, can change growth atmosphere again, even in the situation that use purity not high (analytical pure) raw material, still can effectively control impurity and enter crystal, can effectively solve crystal because the extrinsic absorption of ultraviolet that impurity produces.
Summary of the invention
The purpose of this invention is to provide a kind of molten-salt growth method crystal growth and used airtight monocrystal growing furnace, can change growth atmosphere.The present invention combines the characteristics of common molten salt furnace and lifting furnace, has both satisfied the molten-salt growth method crystal needed little temperature ladder of growing, and can change growth atmosphere again, enters lattice thereby effectively controlled some impurity, improves some optical property of crystal.
Realize that technical scheme of the present invention is as follows:
Airtight monocrystal growing furnace is used in molten-salt growth method crystal growth provided by the invention, and 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 on every side;
Be positioned at described ceramic jacket tubular type burner hearth 1 peripheral and described ceramic jacket tubular type burner hearth 1 surrounded its outer furnace shell 3 of stainless steel;
Pad is loaded on the insulating brick between outer furnace shell 3 inner bottom parts of described stainless steel and the described ceramic jacket tubular type burner hearth 1;
Load outside described stainless steel the fire resistant heat preserving between the furnace shell 3 and described ceramic jacket tubular type burner hearth 1 outer wall cotton;
Pass the thermopair 7 that outer furnace shell 3 outer walls of described stainless steel extend described ceramic jacket tubular type burner hearth 1 outer wall;
Be placed on the fireproof insulation brick bell 2 of described ceramic jacket tubular type burner hearth 1 upper port and fire resistant heat preserving cotton upper end; Be provided with the first vertical central through hole that penetrates for seed rod in the middle of the described fireproof insulation brick bell 2; The described first vertical central through hole both sides are respectively equipped with crystal observation on Growth hole; 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, is provided with the airtight runner that is connected in bucket wall, the bucket end and the bung of the outer furnace shell of described airtight barrel-shaped hollow double-layer stainless steel; In its airtight runner the water coolant that circulates is housed;
The furnace wall of the outer furnace shell 3 of described stainless steel is provided with the bleeding point 4 and the inlet mouth 5 that leads within the described ceramic jacket tubular type burner hearth 1 that leads within the outer furnace shell 3 of described stainless steel; Described bleeding point 4 links to each other 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 the described fireproof insulation brick bell 2; The both sides of described the second vertical central through hole are respectively equipped with the silica glass window 8 relative with described crystal observation on Growth hole;
Be full of atmosphere gas gas in the outer furnace shell 3 of described stainless steel;
Be located at the magnetic fluid 6 of outer furnace shell 3 tops of described stainless steel, the employing corrugated tube is connected between the bung of described magnetic fluid 6 and the outer furnace shell 3 of described stainless steel; The seed rod lower end is passed the second vertical central through hole of the outer furnace shell 3 of magnetic fluid 6, corrugated tube and stainless steel successively and the first vertical central through hole on the insulating brick bell 2 arrives the crucible top; The seed rod upper end is passed magnetic fluid 6 and is connected with universal knot, is fixed in the brilliant rotary head by universal knot.
Described ceramic jacket tubular type burner hearth 1 is 300-500mm highly, and internal diameter is at 80mm-150mm.
Described fireproof insulation brick bell 2 is that two fireproof insulation brick docking form; Distance between outer furnace shell 3 bungs of described fireproof insulation brick bell 2 upper surfaces and 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 diameters are 60-100mm.
Suit one non-airtight stainless steel furnace shell 9 outside the described fire resistant heat preserving cotton; Be provided with space layer between outer furnace shell 3 inwalls of described non-airtight stainless steel furnace shell 9 and described stainless steel; Outer furnace shell 3 inner chambers of described stainless steel, non-airtight stainless steel furnace shell 9 and ceramic jacket tubular type burner hearth 1 interior filling atmosphere gas gas.
S type platinum rhodium thermocouple or K type armoured thermocouple that described thermopair 7 has silica tube to seal for cover; The negative pole of described K type armoured thermocouple is nisiloy, the just very nickel chromium triangle of described K type armoured thermocouple.
The outer furnace shell 3 interior vacuum tightnesss of described stainless steel reach 10
-6Pa, behind the filling atmosphere gas gas, outer furnace shell 3 internal pressures of stainless steel are in (0＜P＜2 standard atmospheric pressure) scope.
It is O that described atmosphere is enclosed 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 stainless steel below, outer furnace shell 3 sides and top, above and below or are on the different positions of sustained height.
When using molten-salt growth method crystal growth of the present invention with airtight monocrystal growing furnace growing crystal, concrete steps are: at first raw material and the solubility promoter with growing crystal mixes according to a certain ratio, in retort furnace, be fused to platinum crucible in batches, then stir, solution is mixed; After the cooling, platinum crucible is placed the ceramic jacket tubular type burner hearth 1 interior suitable position of airtight monocrystal growing furnace of the present invention; The fireproof insulation brick bell 2 that is positioned on ceramic jacket tubular type burner hearth 1 port is formed by two fireproof insulation brick docking, and the center has the first vertical central through hole that penetrates for seed rod; The described first vertical central through hole both sides are respectively equipped with crystal observation on Growth hole; The end that seed rod is equipped with seed crystal passes magnetic fluid 6 successively, corrugated tube, the first vertical central through hole of the second vertical central through hole and fireproof insulation brick bell 2 arrives the crucible top, and the seed rod the other end (upper end) is connected with universal knot, is fixed in the brilliant rotary head; Close inlet mouth 5, open mechanical pump, slowly open again bleeding point 4, vacuumize, bleed complete, close first vacuum valve, close again off-gas pump, open inlet mouth 5, slowly inject required atmosphere gas gas; On this basis, heating schedule is set, the temperature that slowly raises makes the melt fusing, then is cooled near the temperature of saturation, moves seed rod by corrugated tube, makes seed crystal contact liquid level, and slow cooling carries out the crystal growth; After growth finished, then the setting program slow cooling opened inlet mouth 5 to room temperature, injected air, made the pressure in the outer furnace shell 3 of stainless steel return to normal pressure, opened the bell of the outer furnace shell 3 of stainless steel again, took out crystal.
Molten-salt growth method crystal growth of the present invention can be used for the crystal growth of top-seeded solution growth or middle part seed crystal method with airtight monocrystal growing furnace, crystal growing process is that those skilled in the art understand, use said apparatus can prepare various functional crystal materials, these all do not exceed the spirit and scope of the present invention.
Use molten-salt growth method crystal of the present invention to grow with airtight monocrystal growing furnace growing crystal, its effect shows: because the growth of this molten-salt growth method crystal is an airtight crystal growing furnace with airtight monocrystal growing furnace, can change the atmosphere of growth system, broken the restriction that common molten-salt growth method crystal growth can only be carried out under air atmosphere; By injecting extraordinary atmosphere gas gas, at high temperature atmosphere gas gas and foreign ion generation chemical reaction can change the foreign ion radius, and control impurity enters lattice, reaches removal impurity, improves the purpose of some optical property of crystal; Grow with airtight monocrystal growing furnace growing crystal with molten-salt growth method crystal of the present invention, the extrinsic absorption of ultraviolet that can effectively remove some non-linear optic crystals, some other optical property all is improved.
Description of drawings
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 adopts molten-salt growth method crystal growth of the present invention to see through the spectrum comparison diagram with the ultraviolet of airtight monocrystal growing furnace and common Flux Growth Furnace growth KABO crystal;
Fig. 4 adopts molten-salt growth method crystal growth of the present invention to see through the spectrum comparison diagram with the ultraviolet of airtight monocrystal growing furnace and common Flux Growth Furnace growth YAB crystal;
Specific implementation method:
The present invention will be further described below in conjunction with drawings and Examples, and these embodiment only are used for explanation the present invention, are not limited to this.
Embodiment 1:
The airtight monocrystal growing furnace of molten-salt growth method crystal growth 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 all can), highly be 300mm (300-500mm all can), and directly fill the fire resistant heat preserving cotton between the outer furnace shell 3 of stainless steel; The outer furnace shell 3 internal diameter 350mm of stainless steel (300-700mm all can), high 450mm (400-800mm all can); The outer furnace shell of airtight barrel-shaped hollow double-layer stainless steel that the outer furnace shell 3 of this stainless steel is made for the double layer hollow stainless steel is provided with the airtight runner that is connected in its barrel wall, the bucket end and the bung; In its airtight runner the water coolant that circulates is housed; Bleeding point 4 is positioned at outer furnace shell 3 sidewalls of stainless steel top, and inlet mouth 5 is positioned at outer furnace shell 3 sidewalls of stainless steel below; The S type platinum rhodium thermocouple that thermopair 7 seals for outer surface cover silica tube; Ceramic jacket tubular type burner hearth 1 top is by two fireproof insulation brick bells 2 of forming of docking, and the bell center is provided with first vertical central through hole Φ=12mm (between the 10-20mm all can), and respectively there is a crystal observation on Growth hole both sides of the first vertical central through hole; Fireproof insulation brick bell 2 is 90mm (80-200mm all can) apart from the bung of the outer furnace shell 3 of stainless steel distance; The employing corrugated tube is connected between the outer furnace shell 3 of stainless steel and the magnetic fluid 6, can move up and down seed rod, is 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 first vertical central through hole on the 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 observation on Growth hole, by silica glass window 8 and described crystal observation on Growth hole, can observe the growing state of seed crystal.
Adopt embodiment 1 described device, top-seeded solution growth growth K
2Al
2B
2O
7(KABO) crystal.
Take by weighing 207g high-purity (99.99%) K
2CO
3, 152g high-purity (99.99%) Al
2O
3, 204g high-purity (99.99%) H
3BO
3, 107g high-purity (99.99%) NaF, fully ground and mixed is even in agate mortar, get part and place platinum crucible (Φ 80 * Φ 90), slowly be warming up to 500 ℃ in retort furnace, constant temperature a few hours fully discharge gas, and then slowly be warming up to 900 ℃, make the raw material fusing.Through reinforced several times, raw material all is fused in the crucible.Platinum crucible is at first put into common fused salt crystal growing furnace, is warming up to 900 ℃, stirs 24h with the platinum agitator arm.After stirring complete cooling, crucible is placed in the ceramic jacket tubular type burner hearth 1, furnace mouth adds two fireproof insulation brick bells 2.Seed rod one end passes the second vertical central through hole of the outer furnace shell 3 of magnetic fluid 6, corrugated tube and stainless steel and the first vertical central through hole on the insulating brick bell 2 arrives the crucible top; The seed rod the other end passes magnetic fluid 6 and is connected with universal knot, is fixed on brilliant rotary head by universal knot.
Install, close inlet mouth 5, open mechanical pump, slowly open again bleeding point 4, vacuumize, bleed empty complete, close first vacuum valve, close again off-gas pump.Then open inlet mouth 5, slowly inject desired gas (N
2Gas), make the outer furnace shell 3 interior pressure of stainless steel reach 0.5 standard atmospheric pressure.Heating schedule is set, and 20h is warming up to 900 ℃, and along with temperature raises, outer furnace shell 3 internal pressures of stainless steel also increase slightly, remain at last 0.55 standard atmospheric pressure.Keep 24h under the high temperature, then be cooled near the temperature of saturation with 10 ℃/h, by corrugated tube compression decline seed rod, make seed crystal contact liquid level, whether melt-off is determined temperature of saturation by observing crystal.Be higher than about 5 ℃ of temperature of saturation, making seed crystal contact liquid level, then the part melt back is cooled to temperature of saturation, begins the crystal growth with 0.1-0.2 ℃/day rate of temperature fall, and the seed rod rotating speed is 15-20rpm, the positive and negative alternate rotation.Grow after 50 days, obtain the KABO crystal and be of a size of 40 * 22 * 12mm
3, crystal is transparent, without cracking.Ultraviolet sees through spectrum and shows that crystal does not have extrinsic photoabsorption in the 200-300nm zone.
And use above-mentioned same parameter and condition at the KABO crystal of common molten salt furnace growth, and to distinguish though the growth morphology nothing is obvious, there is serious photoabsorption in the crystal of growth at ultraviolet band; The transmitance comparison diagram of KABO crystal as shown in Figure 3, crystal thickness consistent (d=3mm), a is the spectrum that sees through of the crystal of growing in common growth furnace, b is the spectrum that sees through of the crystal of growing in airtight monocrystal growing furnace of the present invention.
Embodiment 2:
The airtight monocrystal growing furnace of molten-salt growth method crystal growth of the present embodiment, as shown in Figure 1, it comprises: ceramic jacket tubular type burner hearth 1 internal diameter is 110mm (80mm-150mm), highly is 350mm (300-500mm all can), and directly fills the fire resistant heat preserving cotton between the outer furnace shell 3 of stainless steel; The outer furnace shell 3 internal diameter 400mm of stainless steel (300-700mm all can), high 500mm (400-800mm all can), the outer furnace shell 3 of stainless steel is the outer furnace shell of airtight barrel-shaped hollow double-layer stainless steel of being made by the double layer hollow stainless steel, is provided with the airtight runner that is connected in its barrel wall, the bucket end and the bung; In its airtight runner the water coolant that circulates is housed; Bleeding point 4 is positioned at outer furnace shell 3 sidewalls of stainless steel top, and inlet mouth 5 is positioned at outer furnace shell 3 sidewalls of stainless steel below.The S type platinum rhodium thermocouple that thermopair 7 seals for outer surface cover silica tube; The fireproof insulation brick bell 2 that burner hearth top is comprised of two docking, centre are established the first vertical central through hole (Φ=15mm, between the 10-20mm all can), and respectively there is a crystal observation on Growth hole both sides; Fireproof insulation brick bell 2 is 95mm (80-200mm all can) apart from the bung of the outer furnace shell 3 of stainless steel distance; Be connected with corrugated tube between the outer furnace shell 3 of stainless steel and the 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 first vertical central through hole on the 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 observation on Growth hole, by silica glass window 8 and described crystal observation on Growth hole, can observe the growing state of seed crystal.
Adopt embodiment 2 described devices, top-seeded solution growth growth YAl
3(BO
3)
4(YAB) crystal.
Take by weighing 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, fully ground and mixed is even in agate mortar, gets part and places platinum crucible (Φ 70 * Φ 90), slowly is warming up to 500 ℃ in retort furnace, and constant temperature a few hours fully discharge gas, and then slowly are warming up to 1200 ℃, make the raw material fusing.Through reinforced several times, raw material all is fused in the crucible.Platinum crucible is at first put into common fused salt crystal growing furnace, is warming up to 1150 ℃, stirs 24h with the platinum agitator arm.After stirring complete cooling, crucible is placed in the 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 that two docking form.Seed rod one end passes the second vertical central through hole of the outer furnace shell 3 of magnetic fluid 6, corrugated tube and stainless steel successively and the first vertical central through hole on the fireproof insulation brick bell 2 arrives the crucible top; The seed rod the other end passes magnetic fluid 6 and is connected with universal knot, is fixed on brilliant rotary head by universal knot.
Install, close inlet mouth 5, open mechanical pump, slowly open again bleeding point 4, vacuumize, bleed complete, close first vacuum valve, close again off-gas pump.Placed several hours, pressure increases slowly, then remains unchanged, and illustrates that the outer furnace shell 3 interior stopping propertys of stainless steel are good.Then open inlet mouth 5, slowly inject desired gas (Ar+H2 mixed gas), make the outer furnace shell 3 interior pressure of stainless steel reach 0.6 standard atmospheric pressure.Heating schedule is set, and 24h is warming up to 1150 ℃, and along with temperature raises, pressure also increases slightly, remains at last 0.7 standard atmospheric pressure.Keep 24h under the high temperature, then be cooled near the temperature of saturation with 10 ℃/h, by corrugated tube compression decline seed rod, make seed crystal contact liquid level, whether melt-off is determined temperature of saturation by observing crystal.Be higher than about 5 ℃ of temperature of saturation, making seed crystal contact liquid level, then the part melt back is cooled to temperature of saturation, and then beginning is increased to the speed cooling of 1-2 ℃/d with the speed cooling of 0.1-0.2 ℃/d, carries out the crystal growth, and the seed rod rotating speed is 15-20rpm.Grow after 60 days, obtain the YAB crystal and be of a size of 30 * 30 * 25mm
3, heavy 46g, the most of zone of crystal is transparent, without cracking.Ultraviolet sees through spectrum and shows that crystal does not have extrinsic photoabsorption in the 200-300nm zone.
And at the YAB crystal of common molten salt furnace growth, growth morphology is without obvious difference, but there is serious photoabsorption in the YAB crystal of common molten salt furnace growth at ultraviolet band.The transmitance comparison diagram of YAB crystal as shown in Figure 4, crystal thickness consistent (d=2.5mm), a is the spectrum that sees through of the crystal of growing in common flux growth stove, b is the spectrum that sees through of the crystal of growing in airtight monocrystal growing furnace of the present invention.
Embodiment 3:
The airtight growth furnace that is used for growth 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), highly is 380mm (300-500mm all can), suit one non-airtight stainless steel furnace shell 9 outside the fire resistant heat preserving cotton; Be provided with space layer between outer furnace shell 3 inwalls of this non-airtight stainless steel furnace shell 9 and stainless steel; Outer furnace shell 3 inner chambers of described stainless steel, non-airtight stainless steel furnace shell 9 and ceramic jacket tubular type burner hearth 1 interior filling atmosphere gas gas; Fireproof insulation brick bell 2 is placed in ceramic jacket tubular type burner hearth 1 top, and the centre is provided with the first vertical central through hole (Φ=16mm, between the 10-20mm all can), and respectively there is a crystal observation on Growth hole its both sides; The outer furnace shell 3 internal diameter 450mm of stainless steel (300-700mm all can), high 550mm (400-800mm all can), the outer furnace shell 3 of stainless steel is the outer furnace shell of airtight barrel-shaped hollow double-layer stainless steel of being made by the double layer hollow stainless steel, is provided with the airtight runner that is connected in its barrel wall, the bucket end and the bung; In its airtight runner the water coolant that circulates is housed; Bleeding point 4 is positioned at outer furnace shell 3 sidewalls of stainless steel below, and inlet mouth 5 is positioned at outer furnace shell 3 sidewalls of stainless steel top; 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 all can) apart from the bung of the outer furnace shell 3 of stainless steel distance; Be connected with corrugated tube between the outer furnace shell 3 of stainless steel and the magnetic fluid 6, can move up and down seed rod, be convenient to adjustable range; Be connected with corrugated tube between the outer furnace shell 3 of stainless steel and the 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 first vertical central through hole on the 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 observation on Growth hole, by silica glass window 8 and described crystal observation on Growth hole, can observe the growing state of seed crystal.
Adopt embodiment 3 described devices, top-seeded solution growth growth BABF crystal.
Take by weighing 175g high-purity (99.99%) BaF
2, 51g high-purity (99.99%) Al
2O
3, 35g high-purity (99.99%) H
3BO
3, 42g high-purity (99.99%) NaF, fully ground and mixed is even in agate mortar, get part and place platinum crucible (Φ 80 * Φ 80), slowly be warming up to 500 ℃ in retort furnace, constant temperature a few hours fully discharge gas, and then slowly be warming up to 950 ℃, make the raw material fusing.Through reinforced several times, raw material all is fused in the crucible.Platinum crucible is at first put into common fused salt crystal growing furnace, is warming up to 950 ℃, stirs 24h.After stirring complete cooling, crucible is placed in the ceramic jacket tubular type burner hearth 1, furnace mouth adds two fireproof insulation brick bells 2.Seed rod one end passes the second vertical central through hole of the outer furnace shell 3 of magnetic fluid 6, corrugated tube and stainless steel and the first vertical central through hole on the insulating brick bell 2 arrives the crucible top; The seed rod the other end passes magnetic fluid 6 and is connected with universal knot, is fixed on brilliant rotary head by universal knot.
Install, close inlet mouth 5, open mechanical pump, slowly open again bleeding point 4, vacuumize, bleed complete, close first vacuum valve, close again off-gas pump.Open inlet mouth 5, then slowly inject desired gas (N
2+ H
2Mixed gas), making the outer furnace shell 3 interior pressure of stainless steel is 1.1 standard atmospheric pressures.Heating schedule is set, and 20h is warming up to 950 ℃, and along with temperature raises, pressure also increases slightly, remains at last 115 standard atmospheric pressures.Keep 20h under the high temperature, make to mix, then be cooled near the temperature of saturation with 10 ℃/h, by corrugated tube compression decline seed rod, make seed crystal contact liquid level, whether melt-off is determined temperature of saturation by observing crystal.Be higher than about 5 ℃ of temperature of saturation, making seed crystal contact liquid level, the part melt back, then be cooled to temperature of saturation, begin the crystal growth with 0.1-0.2 ℃/d rate of temperature fall, the seed rod rotating speed is 15-20rpm, after growth in 45 days, obtain the BABF crystal and be of a size of 15 * 10 * 20mm
3, crystal is transparent, and without inclusion, ultraviolet sees through spectrum and shows that crystal does not have extrinsic photoabsorption in the 200-300nm zone.
And at the BABF crystal of common molten salt furnace growth, growth morphology is without obvious difference, but there is serious photoabsorption in crystal at ultraviolet band; See through spectral class and be similar to Fig. 3 and 4.
Claims (10)
1. airtight monocrystal growing furnace is used in a molten-salt growth method crystal growth, and 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 on every side;
Be positioned at described ceramic jacket tubular type burner hearth (1) stainless steel peripheral and that described ceramic jacket tubular type burner hearth (1) is surrounded it furnace shell (3) outward;
Pad is loaded on the insulating brick between outer furnace shell (3) inner bottom part of described stainless steel and the described ceramic jacket tubular type burner hearth (1);
The fire resistant heat preserving of loading between furnace shell outside described stainless steel (3) and described ceramic jacket tubular type burner hearth (1) outer wall is cotton; Pass the thermopair (7) that outer furnace shell (3) outer wall of described stainless steel extends described ceramic jacket tubular type burner hearth (1) outer wall;
Be placed on the fireproof insulation brick bell (2) of described ceramic jacket tubular type burner hearth (1) upper port and fire resistant heat preserving cotton upper end; Be provided with the first vertical central through hole that penetrates for seed rod in the middle of the described fireproof insulation brick bell (2); The described first vertical central through hole both sides are respectively equipped with crystal observation on Growth hole; 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, is provided with the airtight runner that is connected in bucket wall, the bucket end and the bung of the outer furnace shell of described airtight barrel-shaped hollow double-layer stainless steel; In its airtight runner the water coolant that circulates is housed;
The furnace wall of the outer furnace shell (3) of described stainless steel is provided with the bleeding point (4) that leads to outer furnace shell (3) inner chamber of described stainless steel and leads to inlet mouth (5) within the described ceramic jacket tubular type burner hearth (1); Described bleeding point (4) links to each other 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 the 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 observation on Growth hole;
Be full of atmosphere gas gas in the outer furnace shell (3) of described stainless steel;
Be located at the magnetic fluid (6) of the outer furnace shell (3) of described stainless steel top, adopt corrugated tube to be connected between the bung of described magnetic fluid (6) and the outer furnace shell (3) of described stainless steel; The seed rod lower end is passed the second vertical central through hole of the outer furnace shell (3) of magnetic fluid (6), corrugated tube and stainless steel successively and the first vertical central through hole on the insulating brick bell (2) arrives the crucible top; The seed rod upper end is passed magnetic fluid (6) and is connected with universal knot, is fixed in the brilliant rotary head by universal knot.
2. use airtight monocrystal growing furnace by molten-salt growth method crystal growth claimed in claim 1, it is characterized in that, described ceramic jacket tubular type burner hearth (1) is 300-500mm highly, and internal diameter is at 80mm-150mm.
3. use airtight monocrystal growing furnace by molten-salt growth method crystal growth claimed in claim 1, it is characterized in that, described fireproof insulation brick bell (2) is that two fireproof insulation brick docking form; Distance between outer furnace shell (3) bung of described fireproof insulation brick bell (2) upper surface and described stainless steel is at 80-200mm.
4. use airtight monocrystal growing furnace by molten-salt growth method crystal growth claimed in 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. use airtight monocrystal growing furnace by molten-salt growth method crystal growth claimed in claim 1, it is characterized in that, silica glass window (8) diameter is 60-100mm.
6. use airtight monocrystal growing furnace by molten-salt growth method crystal growth claimed in claim 1, it is characterized in that, suit one non-airtight stainless steel furnace shell (9) outside the described fire resistant heat preserving cotton; Be provided with space layer between outer furnace shell (3) inwall of described non-airtight stainless steel furnace shell (9) and described stainless steel; Outer furnace shell (3) inner chamber of described stainless steel, non-airtight stainless steel furnace shell (9) and the interior filling atmosphere of ceramic jacket tubular type burner hearth (1) gas gas.
7. use airtight monocrystal growing furnace by molten-salt growth method crystal growth claimed in claim 1, it is characterized in that S type platinum rhodium thermocouple or K type armoured thermocouple that described thermopair (7) has silica tube to seal for cover; The negative pole of described K type armoured thermocouple is nisiloy, the just very nickel chromium triangle of described K type armoured thermocouple.
8. use airtight monocrystal growing furnace by molten-salt growth method crystal growth claimed in claim 1, it is characterized in that, the outer interior vacuum tightness of furnace shell (3) of described stainless steel reaches 10
-6Pa, behind the filling atmosphere gas gas, outer furnace shell (3) internal pressure of stainless steel is in (0＜P＜2 standard atmospheric pressure) scope.
9. use airtight monocrystal growing furnace by molten-salt growth method crystal growth claimed in 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 molten-salt growth method crystal growth claimed in claim 1, it is characterized in that, described bleeding point (4) and inlet mouth (5) lay respectively at stainless steel below, outer furnace shell (3) side and top, above and below or are on the different positions of sustained height.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201110195895.5A CN102877116B (en) | 2011-07-13 | 2011-07-13 | Closed monocrystalline growth furnace for molten salt method crystal growth |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201110195895.5A CN102877116B (en) | 2011-07-13 | 2011-07-13 | Closed monocrystalline growth furnace for molten salt method crystal growth |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN102877116A true CN102877116A (en) | 2013-01-16 |
| CN102877116B CN102877116B (en) | 2014-12-31 |
Family
ID=47478624
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201110195895.5A Active CN102877116B (en) | 2011-07-13 | 2011-07-13 | Closed monocrystalline growth furnace for molten salt method crystal growth |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN102877116B (en) |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103386493A (en) * | 2013-07-19 | 2013-11-13 | 江西悦安超细金属有限公司 | Preparation method of carbonyl iron phosphate powder for diamond tool |
| CN106283175A (en) * | 2016-09-22 | 2017-01-04 | 中国科学院理化技术研究所 | A kind of growth nonlinear optical crystal LiB3o5, CsB3o5and CsLiB6o10method |
| CN107557861A (en) * | 2017-10-21 | 2018-01-09 | 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 |
| CN112567076A (en) * | 2019-08-21 | 2021-03-26 | 眉山博雅新材料有限公司 | Open type temperature field |
| CN112771213A (en) * | 2020-06-05 | 2021-05-07 | 眉山博雅新材料有限公司 | Method and apparatus for high uniformity crystal growth without annealing |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| US20060037531A1 (en) * | 2004-08-20 | 2006-02-23 | Fredholm Michele M | Furnace purification and metal fluoride crystals grown in a purified 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 Czochralski method from melt |
-
2011
- 2011-07-13 CN CN201110195895.5A patent/CN102877116B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| US20060037531A1 (en) * | 2004-08-20 | 2006-02-23 | Fredholm Michele M | Furnace purification and metal fluoride crystals grown in a purified 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 Czochralski method from melt |
Cited By (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103386493A (en) * | 2013-07-19 | 2013-11-13 | 江西悦安超细金属有限公司 | Preparation method of carbonyl iron phosphate powder for diamond tool |
| CN106283175A (en) * | 2016-09-22 | 2017-01-04 | 中国科学院理化技术研究所 | A kind of growth nonlinear optical crystal LiB3o5, CsB3o5and CsLiB6o10method |
| CN106283175B (en) * | 2016-09-22 | 2018-08-24 | 中国科学院理化技术研究所 | A kind of growth nonlinear optical crystal LiB3O5、CsB3O5And CsLiB6O10Method |
| CN107557861A (en) * | 2017-10-21 | 2018-01-09 | 福州大学 | A kind of growing method and its process units suitable for BPOC monocrystalline |
| 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 |
| CN112567076A (en) * | 2019-08-21 | 2021-03-26 | 眉山博雅新材料有限公司 | Open type temperature field |
| US20210207285A1 (en) * | 2019-08-21 | 2021-07-08 | Meishan Boya Advanced Materials Co., Ltd. | Temperature field device comprising a first drum, a second drum, and a filler inside the second drum and a space between the second drum and the first drum |
| CN112567076B (en) * | 2019-08-21 | 2021-11-16 | 眉山博雅新材料股份有限公司 | Open type temperature field |
| 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 |
| US11441233B2 (en) | 2019-08-21 | 2022-09-13 | Meishan Boya Advanced Materials Co., Ltd. | Temperature field device comprising a first drum, a second drum, and a filler inside the second drum and a space between the second drum and the first drum |
| CN112771213A (en) * | 2020-06-05 | 2021-05-07 | 眉山博雅新材料有限公司 | Method and apparatus for high uniformity crystal growth without annealing |
| US11655557B2 (en) | 2020-06-05 | 2023-05-23 | Meishan Boya Advanced Materials Co., Ltd. | Methods and devices for growing crystals with high uniformity without annealing |
Also Published As
| Publication number | Publication date |
|---|---|
| CN102877116B (en) | 2014-12-31 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN102877116B (en) | Closed monocrystalline growth furnace for molten salt method crystal growth | |
| US20190137843A1 (en) | Compound of cesium fluorooxoborate, nonlinear optical crystal of cesium fluorooxoborate, and method of preparation and use thereof | |
| CN104313693B (en) | Yttrium aluminum garnet laser crystal doped growth device, crystal growth furnace and preparation method thereof | |
| CN105734668B (en) | A kind of Ba3P3O10The growing method of Cl monocrystalline | |
| CN101831706B (en) | Growth method of low ultraviolet absorption YA13(BO3)4 crystal | |
| CN101575730A (en) | Method for lifting crystal growth by induction heating in reducing atmosphere | |
| WO2019109366A1 (en) | Method for in-situ injection and synthesis of phosphide by using bearing gas | |
| Route et al. | Growth of AgGaSe2 for infrared applications | |
| CN106400101A (en) | Compound semiconductor monocrystal growing device and method | |
| CN215404647U (en) | Single crystal furnace feeding device | |
| CN208791811U (en) | Crystal growing apparatus | |
| CN110484965A (en) | A kind of gallium oxide crystal and its growing method and grower | |
| CN112410868B (en) | High-quality BIBO crystal growth method | |
| CN116575109A (en) | Infrared nonlinear material BaGa 4 Se 7 Single crystal growth method of (2) | |
| CN108193270B (en) | A kind of ternary brass mine semiconductor crystal arsenic germanium cadmium preparation method | |
| CN213925123U (en) | Quartz crucible for manufacturing monocrystalline silicon | |
| CN104894637B (en) | The grower and growing method of a kind of crystal | |
| KR101467117B1 (en) | Ingot growing apparatus | |
| CN211036174U (en) | Crystal growth device | |
| CN109666968B (en) | Method for producing silicon single crystal | |
| CN207727190U (en) | Hydrothermal crystallization device with alternation thermal field | |
| CN207944167U (en) | Czochralski method CeAlO3Crystal growing apparatus | |
| CN206070038U (en) | A kind of crystal growth by flux method platinum crucible cover | |
| CN111379014A (en) | Crystal growth fluxing agent and crystal growth method | |
| KR20190069056A (en) | Ingot growing apparatus |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant |