CN106149051A - The thermal control Bridgman method single-crystal growing apparatus of fluoride single crystal body and method - Google Patents
The thermal control Bridgman method single-crystal growing apparatus of fluoride single crystal body and method Download PDFInfo
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Abstract
The present invention relates to a kind of thermal control Bridgman method single-crystal growing apparatus and the method for fluoride single crystal body, wherein, system of bf body possesses furnace chamber, center is provided with perforate drop-bottom and the vacuum pipe connected with furnace chamber, the center drilling of drop-bottom is through with the cavity of furnace chamber, furnace chamber and drop-bottom are double-decker, and intermediate course is disposed with cooling water channel；Heating and thermal insulation system is arranged in furnace chamber, possesses thermal insulation board, the heater laying respectively at the upper and lower sides of thermal insulation board and heat protection screen, is formed upper pyrometer district, gradient zones, middle part and three warm areas of bottom low-temperature space by thermal insulation board；Crucible descending system includes that crucible water-cooled support column and crucible decline actuating device, the lower end of crucible water-cooled support column declines actuating device with crucible and is connected, the inside of furnace chamber is stretched into support crucible bracket through the center drilling of drop-bottom in upper end, circulation cooling water in crucible water-cooled support column, flow and the water temperature of the cooling water of crucible water-cooled support column can the most independently regulate and control.
Description
Technical field
The invention belongs to the growing technology field of crystal, specifically, relate to a kind of thermal control Bridgman method single-crystal growing apparatus and the method for fluoride single crystal body.
Background technology
Crystal of fluoride is (such as CaF2、SrF2、MgF2、BaF2And LaF2Deng) it is very important Solid State Laser host material.Compared with oxide-base material, fluoride has a characteristic that crystal of fluoride has the transmission range of non-constant width, can be from far ultraviolet up to mid-infrared；The refractive index ratio of crystal of fluoride is relatively low, can reduce the surface reflectivity using spectrum and the nonlinear effect limited under high intensity laser beam pumping effect as far as possible；Low phonon energy can reduce the nonradiative transition probability between energy level, improves radiative quantum efficiency.Thus, the crystal of fluoride of trivalent rare earth ions doping is the ideal system that people are engaged in the fundamental research work such as crystal structure defects, ion dynamics performance, luminescent properties.Although the heat of most crystal of fluoride and mechanical performance are not as crystalline oxide material, but they are combined with the LD pumping source of low thermal force, are very beneficial for setting up high-power miniaturization all solid state middle low power laser instrument.
At present, it is possible to the technology of industrialization growing large-size crystal of fluoride mainly has temperature gradient method (TGT), Bridgman-Stockbarger method (B-S) and czochralski method (Cz), but has its limitation when growing fluoride single crystal body.
Not having relative movement during Crystal Growth by Temperature Gradient Method between crucible and thermal field, crystallization is completely by diffusive transport, along with the increase latent heat of crystal growth height is difficult to discharge；Growth rate is also difficult to control to simultaneously, constitutional supercooling easily occurs, ultimately results in crystal structure second-rate, it is difficult to obtain large scale optical grade crystal.
The crystalline size of conventional crucibles descent method for growing is than temperature ladder big many of method, but conventional crucibles declines stove seed crystal position and there is no that special cooling process or cooling effect are less desirable at present, causes thermograde less than normal.Relatively low at the general ratio again of thermal conductivity plus Fluoride Laser Crystals, so the latent heat at crystal growth initial stage is difficult to be conducted by seed crystal efficiently, easily there is polycrystalline nucleation in the shouldering initial stage；And along with the release advancing latent heat of solid liquid interface becomes more difficult, cause solid liquid interface often in recessed interface and with bigger temperature fluctuation, cause solute Distribution the most uneven and the increase of crystal defect.
Much less than first two of the fluoride single crystal body size of Czochralski grown, and owing to the crystal thermal stress of the temperature bigger growth of field gradient is the biggest many, be difficult to obtain large scale optical grade monocrystal.
In sum, current crystal growing technology all can not effectively solve a difficult problem for the latent heat release difficulty produced during growing large-size fluoride single crystal body.Cause solid liquid interface in crystal growing process to be difficult to control to, temperature fluctuation relatively big, cause the skewness of dopant ion, have a strong impact on the crystalline quality of crystal.
Summary of the invention
For prior art exist fluoride single crystal bulk-growth time latent heat release difficulty, solid liquid interface is often in recessed interface and the problem of instability, it is desirable to provide the thermal control Bridgman method single-crystal growing apparatus of a kind of fluoride single crystal body and method, discharge difficult problem with latent heat during solving large scale fluoride single crystal bulk-growth；In conjunction with rational technological parameter, it is ensured that along with the propelling solid liquid interface of crystal growth is all the time in dimpling shape, improve the crystalline quality of fluoride single crystal body.
For achieving the above object, an aspect of of the present present invention, provide the thermal control Bridgman method single-crystal growing apparatus of a kind of fluoride single crystal body, including: system of bf body, heating and thermal insulation system and crucible descending system, described system of bf body possesses furnace chamber, center is provided with perforate drop-bottom and the vacuum pipe connected with described furnace chamber, the center drilling of described drop-bottom is through with the cavity of described furnace chamber, and described furnace chamber and described drop-bottom are double-decker, and intermediate course is disposed with cooling water channel；Described heating and thermal insulation system is arranged in described furnace chamber, possesses thermal insulation board, the heater laying respectively at the upper and lower sides of described thermal insulation board and heat protection screen, forms upper pyrometer district, gradient zones, middle part and three warm areas of bottom low-temperature space by described thermal insulation board；Described crucible descending system includes that crucible water-cooled support column and crucible decline actuating device, the lower end of described crucible water-cooled support column declines actuating device with described crucible and is connected, the inside of described furnace chamber is stretched into support crucible bracket through the described center drilling of described drop-bottom in upper end, circulation cooling water in described crucible water-cooled support column, flow and the water temperature of the cooling water of described crucible water-cooled support column can the most independently regulate and control.
According to the present invention, suitable thermograde is set up by the way of upper and lower two district's independent heatings, advantageously form stable warm field, in the different phase of crystal growth, crucible water-cooled support column is cooled down discharge and the water temperature real-time monitoring of water, substantially increase the releasability of latent heat so that solid liquid interface more they tends to stable.
Use the thermal control Bridgman method single-crystal growing apparatus of the present invention, the easy polycrystalline growth phenomenon at fluoride combination crystal growth initial stage can be prevented effectively from, solve a difficult problem for crystal growth phase latent heat release difficulty, control the solid-liquid interface shape of crystal growth, be conducive to being uniformly distributed of dopant ion, growing large-size, the fluoride single crystal body of high optical homogeneity.
Also, in the present invention, it is also possible to it is that described crucible water-cooled support column includes the rustless steel water-cooled bar wrapped up by molybdenum pipe, has the gap of 2～4mm between described rustless steel water-cooled bar and the described molybdenum pipe of its periphery.
According to the present invention, molybdenum pipe can shield the high temperature in furnace chamber and directly radiate rustless steel water-cooled bar, strengthens the water-cooled effect of the latter, the beneficially release of latent heat during crystal growth.
Also, in the present invention, it is also possible to being that the material of described furnace chamber is rustless steel, its thickness in monolayer is 6～10mm.
According to the present invention, the material of furnace chamber is rustless steel and its thickness is 6～10mm, thus under fluoride combination crystal growth environment, (fluorine-containing) corrosion resistance is higher, resistance to compression non-deformability is higher.
Also, in the present invention, it is also possible to being that the material of described thermal insulation board is graphite cake, molybdenum plate, tungsten plate or zirconium oxide plate, described heat protection screen includes graphite screen, molybdenum shield, tungsten screen or tungsten-molybdenum combination screen, and described heater includes graphite heating body.
According to the present invention, thermal insulation board selects the heat-barrier material zirconium oxide of the graphite of high reflectance, molybdenum or tungsten material or lower thermal conductivity can strengthen the thermograde of upper and lower two warm areas；Heat protection screen selects the tungsten of high reflectance, Molybdenum metal materials industry, and energy-saving effect is strong, be prone to processing；Graphite heater is prone to processing, low cost.
Also, in the present invention, it is also possible to it is that described crucible bracket is used for fixing crucible, and is zirconium oxide bracket.
According to the present invention, crucible bracket is zirconium oxide bracket, and zirconium oxide can play good heat insulating effect, increases thermograde, strengthens seed crystal thermal conduction effect.
Also, in the present invention, it is also possible to being that the cooling water of described crucible water-cooled support column is provided by single cooling water system, flow and the water temperature of the cooling water that described cooling water system provides can the most independently regulate and control；The modification scope of the flow of described cooling water is 1～8m3/ h, the modification scope of the water temperature of described cooling water is-15～20 DEG C, and fluctuating temperature amplitude is less than 0.2 DEG C.
According to the present invention, the cooling water of crucible water-cooled support column is provided by independent cooling water system, be conducive in the different phase of crystal growth, crucible water-cooled support column being cooled down discharge and the water temperature real-time monitoring of water, substantially increase the releasability of latent heat so that solid liquid interface more they tends to stable.
Another aspect of the present invention, additionally provides a kind of method using above-mentioned thermal control Bridgman method single-crystal growing apparatus to prepare fluoride single crystal body, and described method includes:
(1) fluoride single crystal body raw material is placed in bottom and has in the crucible of seed crystal, on the crucible bracket on the crucible water-cooled support column of the inside that then described crucible is fixed on furnace chamber；
(2) described crucible is risen to the appropriate location of high-temperature region, closes furnace chamber and start evacuation, as vacuum≤5*10-3Material is started to warm up after pa；
(3) regulate the heating power of upper and lower two heaters to set up suitable temperature gradient zone, and the position regulating described crucible makes seed crystal top section melt, and declines described crucible and start crystal growth after constant temperature 5～10h；
(4) gradually tune up the discharge of water-cooled bar along with the growth of crystal, reduce the temperature of cooling water, until isodiametric growth of crystal terminates；
(5) by regulating the heating power of described heater after crystal growth terminates, gradually turn the discharge of described water-cooled bar down, raise the temperature of cooling water, and by regulating the position of described crucible, reduce the thermograde of the upper and lower side of described crucible, it is achieved nearly zero-temperature coefficient Gradient annealing.
The method according to the invention, the gradient magnitude of temperature gradient zone is by being automatically adjusted the formation of the heating power of upper and lower two heaters, during can being prevented effectively from crucible decline, due to the change of the gradient magnitude that the change of bushing position causes.Material process completes in high-temperature region, and crystallization process completes in temperature gradient zone.By regulating heating power and the bushing position of upper and lower two heaters during annealing, nearly zero-temperature coefficient Gradient annealing can be realized, thus be more beneficial for the release of crystal thermal stress.
Also, in the present invention, it is also possible to being that described crucible is graphite crucible, described crucible bracket is outside tungsten or the zirconium oxide bracket of molybdenum sheet parcel.
According to the present invention, wrap up zirconium oxide bracket with tungsten or molybdenum sheet and can effectively shield heat radiation, strengthen the thermal conduction effect of seed crystal.
Also, in the present invention, it is also possible to being that the gradient of described temperature gradient zone is 20～40 DEG C/cm, the decrease speed of described crucible is 0.5～1.5mm/h.
Also, in the present invention, it is also possible to be, grow into during isodiametric growth terminates from crystal shouldering, while gradually tuning up the discharge of described water-cooled bar, reduce the temperature of described cooling water.
Compared with existing Bridgman-Stockbarger method device and growing method, it is an advantage of the current invention that: by the way of upper and lower two district's independent heatings, set up suitable thermograde, advantageously form stable warm field.Particularly crucible water-cooled support column is carried out the design of uniqueness: cooling water is provided by independent cooling water system, in the different phase of crystal growth, crucible water-cooled support column is cooled down discharge and the water temperature real-time monitoring of water, substantially increase the releasability of latent heat so that solid liquid interface more they tends to stable；The outside of crucible water-cooled support column molybdenum pipe wraps up, and the heat that can effectively shield in furnace chamber directly radiates, and significantly enhances the conduction of heat of crucible water-cooled support column.Annealing stage can realize nearly zero-temperature coefficient Gradient annealing, is more beneficial for the release of crystal thermal stress.
According to following detailed description of the invention and with reference to accompanying drawing, it is better understood with foregoing and the other objects, features and advantages of the present invention.
Accompanying drawing explanation
Fig. 1 is the structural representation of the thermal control Bridgman method single-crystal growing apparatus of the fluoride single crystal body of the embodiment according to the present invention；
Fig. 2 is the schematic diagram of the heat-exchange system of the crucible water-cooled support column in the thermal control Bridgman method single-crystal growing apparatus shown in Fig. 1；
Reference: 1, bell-jar furnace chamber；2, drop-bottom；3, vacuum pipe；4, upper heater；5, lower heater；6, upper heat protection screen；7, lower heat protection screen；8, end heat shielding；9, upper temperature-controlling thermal couple；10, lower temperature-controlling thermal couple；11, upper monitoring thermocouple；12, lower monitoring thermocouple；13, crucible；14, thermal insulation board；15, zirconium oxide torr；16, molybdenum pipe；17, rustless steel water-cooled bar；18, crucible declines actuating device；Crucible water-cooled support column 19；Cooling water system 20；Storage tank 21；Refrigeration system 22；Water flow controller 23.
Detailed description of the invention
The present invention is further illustrated, it should be appreciated that accompanying drawing and following embodiment are merely to illustrate the present invention below in conjunction with accompanying drawing and following embodiment, and the unrestricted present invention.
The present invention is directed to latent heat release difficulty during the fluoride single crystal bulk-growth of prior art existence, solid liquid interface is often in recessed interface and the problem of instability, provide the thermal control Bridgman method single-crystal growing apparatus of a kind of fluoride single crystal body, including: system of bf body, heating and thermal insulation system and crucible descending system, described system of bf body possesses furnace chamber, center is provided with the drop-bottom of perforate, and the vacuum pipe connected with described furnace chamber, the center drilling of described drop-bottom is through with the cavity of described furnace chamber, described furnace chamber and described drop-bottom are double-decker, intermediate course is disposed with cooling water channel；Described heating and thermal insulation system is arranged in described furnace chamber, possesses thermal insulation board, the heater laying respectively at the upper and lower sides of described thermal insulation board and heat protection screen, forms upper pyrometer district, gradient zones, middle part and three warm areas of bottom low-temperature space by described thermal insulation board；Described crucible descending system includes that crucible water-cooled support column and crucible decline actuating device, the lower end of described crucible water-cooled support column declines actuating device with described crucible and is connected, the inside of described furnace chamber is stretched into support crucible bracket through the described center drilling of described drop-bottom in upper end, circulation cooling water in described crucible water-cooled support column, flow and the water temperature of the cooling water of described crucible water-cooled support column can the most independently regulate and control.
According to the present invention, suitable thermograde is set up by the way of upper and lower two district's independent heatings, advantageously form stable warm field, in the different phase of crystal growth, crucible water-cooled support column is cooled down discharge and the water temperature real-time monitoring of water, substantially increase the releasability of latent heat so that solid liquid interface more they tends to stable.
Fig. 1 shows the structural representation of the thermal control Bridgman method single-crystal growing apparatus of the fluoride single crystal body of the embodiment according to the present invention.
The thermal control Bridgman method single-crystal growing apparatus of this embodiment as shown in Figure 1, including system of bf body, heating and thermal insulation system and crucible descending system.Described system of bf body is airtight system of bf body, has drop-bottom 2 and the vacuum pipe 3 of perforate including furnace chamber 1, center.This furnace chamber 1 is formed as bell-jar furnace chamber, and vacuum pipe 3 connects with furnace chamber 1.The center drilling of drop-bottom 2 is through with the cavity of furnace chamber 1, and furnace chamber 1 and drop-bottom 2 are double-decker, and intermediate course is disposed with cooling water channel.This cooling water channel for example, spiral cooling water channel.
Described heating and thermal insulation system includes thermal insulation board 14, upper and lower two independent heaters 4,5 and heat protection screen 6,7, forms upper pyrometer district A, gradient zones, middle part B and tri-warm areas of bottom low-temperature space C.High-temperature region A be the region on thermal insulation board 14, low-temperature space C be the region under thermal insulation board 14, gradient zones B is the region near thermal insulation board 14 position.Additionally, end heat shielding 8 also can be provided with in the lower section of bottom low-temperature space C.
Upper and lower two heaters 4,5 can be such as graphite heater, and the heating power of this heater can independently be controlled by upper temperature-controlling thermal couple 9 and lower temperature-controlling thermal couple 10 respectively, and upper monitoring thermocouple 11 and lower monitoring thermocouple 12 can play the effect of monitoring.Rational thermograde can be set up by the value of feedback of upper and lower two temperature-controlling thermal couples 9,10 and two monitoring thermocouple 11,12.During crystal growth, raw material melts at high-temperature region A, crystallizes at gradient zones B, is incubated at low-temperature space C.
Described crucible descending system includes that crucible water-cooled support column 19 and crucible decline actuating device 18.In the embodiment shown in Fig. 1, the rustless steel water-cooled bar 17 that this crucible water-cooled support column 19 can be wrapped up by molybdenum pipe 16 forms, molybdenum pipe 16 can shield the high temperature in furnace chamber 1 and directly radiate rustless steel water-cooled bar 17, strengthens the water-cooled effect of the latter, the beneficially release of latent heat during crystal growth.The lower end of crucible water-cooled support column 19 and crucible decline actuating device 18 and are connected, and upper end passes the center drilling of drop-bottom 2 and stretches into furnace chamber 1 inner support and crucible bracket 15.The cooling water of the crucible water-cooled support column 19 in the present invention is provided by independent cooling water system 20, and discharge and the water temperature of its cooling water can carry out real-time monitoring according to the demand of growth technique.
The cooling water system 20 of the independent crucible water-cooled support column described in this embodiment is as in figure 2 it is shown, include small-sized storage tank 21, refrigeration system 22 and water flow controller 23.It can be 1m that the hot water that crucible water-cooled support column 19 flows out initially enters volume3Small-sized storage tank 21, then flow into storage tank 21 opposite side refrigeration system 22, refrigeration system 22 the cooling water flowed out flows into crucible water-cooled support column 19 after water flow controller 23 again.The water temperature that refrigeration system 20 can flow out according to process requirements regulation, water temperature modification scope is-15～20 DEG C, and fluctuating temperature amplitude is less than 0.2 DEG C.The discharge that water flow controller can flow out according to process requirements regulation, modification scope is 1～8m3/h。
The thermal control Bridgman method single-crystal growing apparatus further describing the fluoride single crystal body of the present invention below according to different embodiments and the method using this device to prepare fluoride single crystal body.
Embodiment
1
Growth CaF2Monocrystal, concrete preparation method is as follows:
By 8Kg CaF2Crystal raw material and 80g PbF2Powder has CaF bottom loading after uniformly mixing2In the crucible 13 of the graphite of crystal seeds, then crucible 13 is fixed on the zirconium oxide bracket 15 on the crucible water-cooled support column 19 within furnace chamber 1, wherein PbF2As oxygen scavenger.Crucible 13 is risen to the appropriate location (seed crystal upper surface is slightly higher than thermal insulation board 14) of high-temperature region A, closes furnace chamber 1 and start evacuation, as vacuum≤5*10-3The ramp material with 50 DEG C/h is started after pa；Constant temperature 10h after the monitoring thermocouple temperature at seed crystal position reaches 800 DEG C, fully to remove the oxygen composition within crucible 13.Then proceed to the ramp of 50 DEG C/h, the thermograde size making temperature gradient zone B by regulating the heating power of upper and lower two heaters 4,5 is 25 DEG C/cm, constant temperature 5 h after the monitoring thermocouple temperature at seed crystal position reaches 1360～1380 DEG C, it is ensured that decline crucible 13 with the speed of 1.2mm/h after raw material is the most melt-blended and start crystal growth.The discharge of crystal growth initial stage water-cooled bar 17 is set to 1.5 m3/ h, temperature is 15 DEG C；During shouldering has just started to terminate this to shouldering, the discharge of water-cooled bar 17 is gradually by 1.5m3/ h increases to 3m3/ h, cooling water temperature are gradually lowered to 10 DEG C by 15 DEG C.During shouldering terminates to terminate this to isodiametric growth, the discharge of water-cooled bar 17 is gradually by 3m3/ h increases to 6m3/ h, cooling water temperature are gradually lowered to 5 DEG C by 10 DEG C.Crystal growth terminate after by regulate upper and lower two heaters 4,5 heating power, gradually turn the discharge of water-cooled bar 17 down, raise cooling water temperature, the position of regulation crucible 13 is to reduce the thermograde of crucible 13 upper and lower side simultaneously, it is achieved nearly zero-temperature coefficient Gradient annealing.
Embodiment
2
Growth Yb, Na:CaF2Monocrystal, concrete preparation method is as follows:
6 Kg Yb, Na are co-doped with CaF2Crystal raw material and 60g
PbF2Powder has CaF bottom loading after uniformly mixing2In the crucible 13 of the graphite of crystal seeds, then crucible 13 is fixed on the zirconium oxide bracket 15 on the crucible water-cooled support column 19 within furnace chamber 1, wherein PbF2As oxygen scavenger.Crucible 13 is risen to the appropriate location (seed crystal upper surface is slightly higher than thermal insulation board 14) of high-temperature region A, closes furnace chamber 1 and start evacuation, as vacuum≤5*10-3The ramp material with 50 DEG C/h is started after pa；Constant temperature 10h after the monitoring thermocouple temperature at seed crystal position reaches 800 DEG C, fully to remove the oxygen composition within crucible 13.Then proceed to the ramp of 50 DEG C/h, the thermograde size making temperature gradient zone B by regulating the heating power of upper and lower two heaters 4,5 is 25 DEG C/cm, constant temperature 10 h after the monitoring thermocouple temperature at seed crystal position reaches 1360～1380 DEG C, it is ensured that decline crucible 13 with the speed of 1 mm/h after raw material is the most melt-blended and start crystal growth.The discharge of crystal growth initial stage water-cooled bar 17 is set to 1.5 m3/ h, temperature is 15 DEG C；During shouldering has just started to terminate this to shouldering, the discharge of water-cooled bar 17 is gradually by 1.5 m3/ h increases to 3.5 m3/ h, cooling water temperature are gradually lowered to 8 DEG C by 15 DEG C.During shouldering terminates to terminate this to isodiametric growth, the discharge of water-cooled bar 17 is gradually by 3.5 m3/ h increases to 6 m3/ h, cooling water temperature are gradually lowered to 1 DEG C by 8 DEG C.Crystal growth terminate after by regulate upper and lower two heaters 4,5 heating power, gradually turn the discharge of water-cooled bar 17 down, raise cooling water temperature, the position of regulation crucible 13 is to reduce the thermograde of crucible 13 upper and lower side simultaneously, it is achieved nearly zero-temperature coefficient Gradient annealing.
Embodiment
3
Growth SrF2Monocrystal, concrete preparation method is as follows:
By 8Kg SrF2Crystal raw material and 80g PbF2Powder has SrF bottom loading after uniformly mixing2In the crucible 13 of the graphite of crystal seeds, then crucible 13 is fixed on the zirconium oxide bracket 15 on the crucible water-cooled support column 19 within furnace chamber 1, wherein PbF2As oxygen scavenger.Crucible 13 is risen to the appropriate location (seed crystal upper surface is slightly higher than thermal insulation board 14) of high-temperature region A, closes furnace chamber 1 and start evacuation, as vacuum≤5*10-3The ramp material with 50 DEG C/h is started after pa；Constant temperature 10h after the monitoring thermocouple temperature at seed crystal position reaches 800 DEG C, fully to remove the oxygen composition within crucible 13.Then proceed to the ramp of 50 DEG C/h, the thermograde size making temperature gradient zone by regulating the heating power of upper and lower two heaters 4,5 is 25 DEG C/cm, constant temperature 6h after the monitoring thermocouple temperature at seed crystal position reaches 1460～1480 DEG C, it is ensured that decline crucible 13 with the speed of 1.5mm/h after raw material is the most melt-blended and start crystal growth.The discharge of crystal growth initial stage water-cooled bar 17 is set to 1.2m3/ h, temperature is 15 DEG C；During shouldering has just started to terminate this to shouldering, the discharge of water-cooled bar 17 is gradually by 1.5m3/ h increases to 3m3/ h, cooling water temperature are gradually lowered to 10 DEG C by 15 DEG C.During shouldering terminates to terminate this to isodiametric growth, the discharge of water-cooled bar 17 is gradually by 3m3/ h increases to 6.5m3/ h, cooling water temperature are gradually lowered to 5 DEG C by 10 DEG C.Crystal growth terminate after by regulate upper and lower two heaters 4,5 heating power, gradually turn the discharge of water-cooled bar 17 down, raise cooling water temperature, the position of regulation crucible 13 is to reduce the thermograde of crucible 13 upper and lower side simultaneously, it is achieved nearly zero-temperature coefficient Gradient annealing.
Embodiment
4
Growth Nd, Y:SrF2Monocrystal, concrete preparation method is as follows:
6Kg Nd, Y are co-doped with SrF2Crystal raw material and 60g
PbF2Powder has SrF bottom loading after uniformly mixing2In the crucible 13 of the graphite of crystal seeds, then crucible 13 is fixed on the zirconium oxide bracket 15 on the crucible water-cooled support column 19 within furnace chamber 1, wherein PbF2As oxygen scavenger.Crucible 13 is risen to the appropriate location (seed crystal upper surface is slightly higher than thermal insulation board 14) of high-temperature region A, closes furnace chamber 1 and start evacuation, as vacuum≤5*10-3The ramp material with 50 DEG C/h is started after pa.Constant temperature 10h after the monitoring thermocouple temperature at seed crystal position reaches 800 DEG C, fully to remove the oxygen composition in raw material.Then proceed to the ramp of 50 DEG C/h, the thermograde size making temperature gradient zone B by regulating the heating power of upper and lower two heaters 4,5 is 30 DEG C/cm, constant temperature 10h after the monitoring thermocouple temperature at seed crystal position reaches 1460～1480 DEG C, it is ensured that decline crucible 13 with the speed of 1mm/h after raw material is the most melt-blended and start crystal growth.The discharge of crystal growth initial stage water-cooled bar 17 is set to 1.5m3/ h, temperature is 15 DEG C；During shouldering has just started to terminate this to shouldering, the discharge of water-cooled bar 17 is gradually by 1.5m3/ h increases to 4 m3/ h, cooling water temperature are gradually lowered to 5 DEG C by 15 DEG C.During shouldering terminates to terminate this to isodiametric growth, the discharge of water-cooled bar 17 is gradually by 4 m3/ h increases to 6.5 m3/ h, cooling water temperature are gradually lowered to 0 DEG C by 5 DEG C.Crystal growth terminate after by regulate upper and lower two heaters 4,5 heating power, gradually turn the discharge of water-cooled bar 17 down, raise cooling water temperature, the position of regulation crucible 13 is to reduce the thermograde of crucible 13 upper and lower side simultaneously, it is achieved nearly zero-temperature coefficient Gradient annealing.
Under the objective without departing from the basic feature of the present invention, the present invention can be presented as various ways, therefore the embodiment in the present invention is to be illustrative rather than definitive thereof, owing to the scope of the present invention is defined by the claims rather than limited by description, and all changes in the scope defined in claim, or the full scope of equivalents of its scope defined that fall are understood to include in detail in the claims.
Claims (10)
1. the thermal control Bridgman method single-crystal growing apparatus of a fluoride single crystal body, it is characterised in that including: system of bf body, heating and thermal insulation system and crucible descending system；
Described system of bf body possesses furnace chamber, center is provided with perforate drop-bottom and the vacuum pipe connected with described furnace chamber, the center drilling of described drop-bottom is through with the cavity of described furnace chamber, described furnace chamber and described drop-bottom are double-decker, and intermediate course is disposed with cooling water channel；
Described heating and thermal insulation system is arranged in described furnace chamber, possesses thermal insulation board, the heater laying respectively at the upper and lower sides of described thermal insulation board and heat protection screen, forms upper pyrometer district, gradient zones, middle part and three warm areas of bottom low-temperature space by described thermal insulation board；
Described crucible descending system includes that crucible water-cooled support column and crucible decline actuating device, the lower end of described crucible water-cooled support column declines actuating device with described crucible and is connected, the inside of described furnace chamber is stretched into support crucible bracket through the described center drilling of described drop-bottom in upper end, circulation cooling water in described crucible water-cooled support column, flow and the water temperature of the cooling water of described crucible water-cooled support column can the most independently regulate and control.
Thermal control Bridgman method single-crystal growing apparatus the most according to claim 1, it is characterized in that, described crucible water-cooled support column includes the rustless steel water-cooled bar wrapped up by molybdenum pipe, has the gap of 2～4mm between described rustless steel water-cooled bar and the described molybdenum pipe of its periphery.
Thermal control Bridgman method single-crystal growing apparatus the most according to claim 1 and 2, it is characterised in that the material of described furnace chamber is rustless steel, its thickness in monolayer is 6～10mm.
Thermal control Bridgman method single-crystal growing apparatus the most according to any one of claim 1 to 3, it is characterized in that, the material of described thermal insulation board is graphite cake, molybdenum plate, tungsten plate or zirconium oxide plate, described heat protection screen includes graphite screen, molybdenum shield, tungsten screen or tungsten-molybdenum combination screen, and described heater includes graphite heating body.
Thermal control Bridgman method single-crystal growing apparatus the most according to any one of claim 1 to 4, it is characterised in that described crucible bracket is used for fixing crucible, and is zirconium oxide bracket.
Thermal control Bridgman method single-crystal growing apparatus the most according to any one of claim 1 to 5, it is characterized in that, the cooling water of described crucible water-cooled support column is provided by single cooling water system, and flow and the water temperature of the cooling water that described cooling water system provides can the most independently regulate and control；The modification scope of the flow of described cooling water is 1～8m3/ h, the modification scope of the water temperature of described cooling water is-15～20 DEG C, and fluctuating temperature amplitude is less than 0.2 DEG C.
7. using the method that thermal control Bridgman method single-crystal growing apparatus according to any one of claim 1 to 6 prepares fluoride single crystal body, described method includes:
(1) fluoride single crystal body raw material is placed in bottom and has in the crucible of seed crystal, on the crucible bracket on the crucible water-cooled support column of the inside that then described crucible is fixed on furnace chamber；
(2) described crucible is risen to the appropriate location of high-temperature region, closes furnace chamber and start evacuation, as vacuum≤5*10-3Material is started to warm up after pa；
(3) regulate the heating power of upper and lower two heaters to set up suitable temperature gradient zone, and the position regulating described crucible makes seed crystal top section melt, and declines described crucible and start crystal growth after constant temperature 5～10h；
(4) gradually tune up the discharge of water-cooled bar along with the growth of crystal, reduce the temperature of cooling water, until isodiametric growth of crystal terminates；
(5) gradually turn the discharge of described water-cooled bar after crystal growth terminates down, raise the temperature of cooling water, and by regulating position and the heating power of described heater of described crucible, reduce the thermograde of the upper and lower side of described crucible, it is achieved nearly zero-temperature coefficient Gradient annealing.
Method the most according to claim 7, it is characterised in that described crucible is graphite crucible, described crucible bracket is outside tungsten or the zirconium oxide bracket of molybdenum sheet parcel.
Method the most according to claim 8, it is characterised in that the gradient of described temperature gradient zone is 20～40 DEG C/cm, the decrease speed of described crucible is 0.5～1.5mm/h.
Method the most according to claim 9, it is characterised in that grow into during isodiametric growth terminates from crystal shouldering, reduce the temperature of described cooling water while gradually tuning up the discharge of described water-cooled bar.
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