CN103060891B - Device and method for directionally growing fluoride single crystal via lifting small-gradient thermal field - Google Patents
Device and method for directionally growing fluoride single crystal via lifting small-gradient thermal field Download PDFInfo
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- CN103060891B CN103060891B CN201310039285.5A CN201310039285A CN103060891B CN 103060891 B CN103060891 B CN 103060891B CN 201310039285 A CN201310039285 A CN 201310039285A CN 103060891 B CN103060891 B CN 103060891B
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Abstract
The invention discloses a device and a method for directionally growing fluoride single crystal via lifting a small-gradient thermal field, which belongs to the technical field of crystal growth. The prior art has low success rate and bad crystal quality. The device disclosed by the invention is characterized in that a crucible is installed on the upper side of the bottom part of an insulating sleeve via a crucible pedestal; electrode holders which are opposite two by two are connected via connection beams, the middle points of the connection beams are intersected on one point, and the connection beams are connected on the point to form a complete body; the low ends of pulling rods are connected with the connection beams on the point; and electrode rods are dynamically matched with sealing rings. The method disclosed by the invention is characterized in that the pulling rods pull the heating bodies via the connection beams, the electrode holders and the electrode rods, later the thermal field is lifted, and finally the crucible, small crystal tubes, the crucible pedestal and small crystals are static. The success rate of the magnesium fluoride crystals grown according to the invention is over 95%, the dislocation density is reduced to 10-30/cm<2>, the absorption coefficient at the wave band of 0.2-7.5 micrometers is smaller than 2*10E-4/cm, and the quality of the crystals is fully improved.
Description
Technical field
The present invention relates to a kind of device and method of little gradient temperature field rising oriented growth fluoride single crystal, grow specific direction fluorochemical under vacuum as magnesium fluoride monocrystalline, belong to technical field of crystal growth.
Background technology
Fluoride single crystal is a kind of crystalline material with anisotropy and birefringent characteristic, is mainly used in ultraviolet band polarization element.Due to the requirement of birefringent characteristic aspect, cutting of crystal must be carried out according to specific direction, if crystal is failed according to pre-determined direction growth, then cut loss large, utilization ratio is low.In order to increase operation rate, must oriented growth crystal.The method of existing oriented growth fluoride single crystal is a kind of young brilliant descent method.The method is growing crystal under vacuum, for magnesium fluoride monocrystalline, magnesium fluoride seed crystal is placed in crucible bottom, and crucible is connected on water-cooled decline bar.At the crystal growth initial stage, the temperature of accurate control seed crystal position and warm field, make seed crystal melt about half, then water-cooled decline bar slowly moves down, crucible is the slowly movement from hot-zone in stove to cold-zone thereupon, and crystal is slowly grown according to the direction that seed crystal is intrinsic.
The requirement of the brilliant descent method of described son to crystal growth equipment and envrionment conditions is very harsh, especially at the crystal growth initial stage, namely magnesium fluoride seed crystal is melted the critical stage of about half, this demands very accurately control temperature.Warm field residing for seed crystal is made up of jointly heating element, crucible, water-cooled decline bar etc., in the middle part of seed crystal, the temperature of residing warm field must to control more than the brilliant fusing point of son 5 ~ 10 degree, the seed crystal first half is melted completely, and seed crystal Lower Half is not melted, and such crystal could normal growth.Adopt existing son brilliant descent method for growing magnesium fluoride monocrystalline, because seed crystal is connected on water-cooled decline bar in crucible bottom by crucible holder, the fluctuation of cooler-water temperature and flow can cause warm field residing for seed crystal to depart from default temperature field, cause seed crystal to melt completely or melt insufficient, both of these case all will cause crystal growth failure.
Another shortcoming of the brilliant descent method of existing son is, due to the existence of water coolant, the temperature of water-cooled decline bar is less than 100 DEG C all the time, and the fusing point of crystal is far above this temperature, and the fusing point as magnesium fluoride crystal is 1255 DEG C, this just makes the warm field gradient of seed crystal position very steep, make when warm field residing in the middle part of seed crystal reaches more than crystalline melting point 5 ~ 10 degree, in crucible, the temperature on top far above crystalline melting point, will cause the volatilization of crystal raw material, even cause raw material excessive in a large number, crystal growth failure.
In a word, the success ratio of existing son brilliant descent method oriented growth fluoride single crystal is adopted to only have 50 ~ 60%.Due to Real Time Observation situation cannot be melted to seed crystal in crystal growing process, cannot examine in time and know whether seed crystal melts according to predetermined requirement, until crystal growing process terminates just can know crystal growth result completely, if failure, the serious waste of starting material and electric energy certainly will be caused.So low success ratio and so serious waste, cause the magnesium fluoride monocrystalline blank price with specific direction on market up to more than 10000 yuan/kilogram, have impact on this material in field application widely.
Although existing son brilliant descent method oriented growth crystal of fluoride still has the success ratio of 50 ~ 60%, also have problems in crystal mass.Due to the existence of water-cooled decline bar, the phenomenons such as appearance temperature fluctuation, warm field shakiness and thermograde are excessive, the negative results of these phenomenons causes the shape of solid-liquid interface not to be desirable smooth convex interface, and then cause matter crystal internal defect to be formed in a large number, and dislocation desity reaches 60 ~ 100/cm
2, uptake factor reaches 5 × 10E-4/cm, and such quality is difficult to the requirement meeting high-end ahrens prism.
Summary of the invention
The object of we's invention is, improves the success ratio of fluoride single crystal oriented growth, improves crystal mass, for this reason, we have invented a kind of device and method of little gradient temperature field rising oriented growth fluoride single crystal.The core of its technical scheme cancels water-cooled decline bar, controls heating element and rise, and young crystalline substance is covert to decline, and warm field is stablized, and thermograde reduces, and overcomes prior art Problems existing comprehensively.
In the device of the little gradient temperature field rising oriented growth fluoride single crystal of the present invention, be muff 2 in vacuum chamber 1 inner peripheral, crucible 3 is positioned at muff 2 center of inside, as shown in Figure 1; Have young brilliant cylinder 4 in crucible 3 bottom centre, young brilliant cylinder 4 is crucible holder 5 below; Several heating members 6 are contour is suspended on crucible 3 lateral wall circumference, and heating member 6 upper end connects water cooled electrode bar 7, and battery lead rod 7 is first connected with electrode holder 9 through the sealing-ring 8 at vacuum chamber 2 top through muff 2 top again; Temperature-control heat couple 10 is positioned at the young brilliant cylinder At The Height in young brilliant cylinder 4 side 1/2 ~ 2/3; It is characterized in that, crucible 3 is placed in above bottom muff 2 through crucible holder 5, as shown in Figure 2; Electrode holder 9 facing each other couples together by each tie-beam 11, and the mid point of each tie-beam 11 intersects at a point, and each tie-beam 11 is connected to each other integral at this point, and the lower end of lifting rod 12 is connected with each tie-beam 11 at this point; Battery lead rod 7 coordinates with sealing-ring 8 is dynamic.
According to the method for the little gradient temperature field rising oriented growth fluoride single crystal of the present invention, as shown in Figure 3, son brilliant 13 is inserted young brilliant cylinder 4, the young upper end of brilliant 13 probes into crucible 3, growth material 14 is loaded crucible 3, the warm field of growth is produced by heating member 6, controlling warm field temperature residing for young brilliant 13 first halves by temperature-control heat couple 10 is the temperature higher than grown fluoride single crystal fusing point 5 ~ 10 DEG C, after brilliant 13 first halves of son melt, young crystalline substance 13 and the upper and lower relative movement in warm field, solid-liquid interface shifts to cold-zone from the hot-zone of warm field, until crystal growth is complete; It is characterized in that, upwards lift heating member 6 by lifting rod 12 by tie-beam 11, electrode holder 9, battery lead rod 7, rises in warm field thereupon, and crucible 3, young brilliant cylinder 4, crucible holder 5, young crystalline substance 13 are static.
Its technique effect of the present invention is, because crucible 3 is placed in above bottom muff 2 through crucible holder 5, eliminate the water-cooled decline bar below crucible holder 5 of the prior art, in crystal growing process, crucible 3, young brilliant cylinder 4, crucible holder 5, young brilliant 13 keep static, relative movement up and down between young brilliant 13 and warm field, solid-liquid interface shifts to cold-zone from the hot-zone of warm field is in other words risen by warm field to realize, and these technical measures can bring many-sided technique effect.Such as, the gradient of the warm field around young brilliant 13 diminishes, and residing for young brilliant 13 first halves, temperature is easy to control, and avoids to a great extent occurring that young brilliant 13 first halves do not melt or young brilliant 13 situations of entirely melting; Warm field temperature residing for young brilliant 13 first halves can be normally kept to be the temperature higher than grown fluoride single crystal fusing point 5 ~ 10 DEG C, a lot of without the need to growth material melt temperature being brought up to more than fluoride single crystal fusing point, thus can alleviate the volatilization of crystal raw material, avoid raw material excessive in a large number.Therefore the success ratio of final crystal growth can bring up to more than 95%.For another example, steady, the warm field gradient of growth temperature is close to constant, the shape of solid-liquid interface presents desirable smooth convex interface substantially, significantly reduce matter crystal internal defect, adopt X-ray orientation device directed, orientation accuracy is 30 "; directional precision is for reaching 2 °; be greater than 90% in the maximum 100mm of magnesium fluoride monocrystalline ingot diameters of C direction growth, the availability in length 200mm, C direction, dislocation desity is reduced to 10 ~ 30/cm
2, be less than 2 × 10E-4/cm at the uptake factor of 0.2 ~ 7.5 mu m waveband, crystal mass improves comprehensively.The present invention also has a subsidiary effect, and along with the cancellation of original water-cooled decline bar, cooling structure is simplified.
Accompanying drawing explanation
Fig. 1 is the device one-piece construction schematic diagram of the little gradient temperature field rising oriented growth fluoride single crystal of the present invention.Fig. 2 is device lower part structure enlarged diagram of the little gradient temperature field rising oriented growth fluoride single crystal of the present invention.Fig. 3 is the method schematic diagram of the little gradient temperature field rising oriented growth fluoride single crystal of the present invention, and this figure is simultaneously as Figure of abstract.
Embodiment
In the device of the little gradient temperature field rising oriented growth fluoride single crystal of the present invention, muff 2 in vacuum chamber 1 inner peripheral, muff 2 material is carbon fiber reinforce plastic, crucible 3 is positioned at muff 2 center of inside, crucible 3 adds graphite material crucible cover 15, prevent growth material melt heat loss and stop growth material volatilization, as shown in Figure 1; Have young brilliant cylinder 4 in crucible 3 bottom centre, young brilliant cylinder 4 is crucible holder 5 below, and crucible holder 5 is graphite material; Several heating members 6 are contour is suspended on crucible 3 lateral wall circumference, and heating member 6 upper end connects water cooled electrode bar 7, and battery lead rod 7 is first connected with electrode holder 9 through the sealing-ring 8 at vacuum chamber 2 top through muff 2 top again; Temperature-control heat couple 10 is positioned at the young brilliant cylinder At The Height in young brilliant cylinder 4 side 1/2 ~ 2/3; Crucible 3 is placed in above bottom muff 2 through crucible holder 5, as shown in Figure 2; Electrode holder 9 facing each other couples together by each tie-beam 11, and tie-beam 11 and electrode holder 9 insulate, supply lead receiving electrode seat 9; The mid point of each tie-beam 11 intersects at a point, and each tie-beam 11 is connected to each other integral at this point, and the lower end of lifting rod 12 is connected with each tie-beam 11 at this point; Battery lead rod 7 coordinates with sealing-ring 8 is dynamic, and battery lead rod 7 is red copper material, and hollow water flowing cools, and keeps the vacuum tightness in vacuum chamber 1 by sealing-ring 8.Battery lead rod 7 is connected with the graphite terminal of heating member 6 by bolt and nut.
According to the method for the little gradient temperature field rising oriented growth fluoride single crystal of the present invention, as shown in Figure 3, fritter magnesium fluoride monocrystalline is processed into cylindric as young brilliant 13, seed crystal 13 diameter 15mm, length 65mm, the axis of cylinder be monocrystalline C to, the utilization ratio of the fluoride single crystal crystal ingot grown along this direction is the highest; Son brilliant 13 is inserted young brilliant cylinder 4, and seed crystal cylinder 13 internal diameter matches with seed crystal 13 external diameter, keeps the vertical state of seed crystal 13; The young upper end of brilliant 13 probes into crucible 3.Magnesium fluoride particle growth material 14 is loaded crucible 3.Open rotary-vane vaccum pump and oil diffusion pump successively, vacuum chamber 1 is evacuated to the vacuum of 2 × 10E-3 torr.The warm field of growth is produced by heating member 6, furnace temperature rises to more than magnesium fluoride crystal fusing point 5 ~ 10 DEG C certain temperature namely between 1260 ~ 1265 DEG C by room temperature by temperature rise rate 25 DEG C/h, as 1263 DEG C, growth material 14 is slowly fused into melt, control constant temperature afterwards, within the constant temperature period, melt fully gets rid of gas and other impurity.Warm field temperature residing for young brilliant 13 first halves is controlled on this temperature value by temperature-control heat couple 10.Constant temperature is after 5 hours, young brilliant 13 first halves melt, by lifting rod 12 by tie-beam 11, electrode holder 9, battery lead rod 7 with the speed of 1 ~ 3mm/h as 1mm/h upwards lifts heating member 6, rise in temperature field thereupon, crucible 3, young brilliant cylinder 4, crucible holder 5, young crystalline substance 13 is static, young crystalline substance 13 and the upper and lower relative movement in warm field, the bottom of crucible 3, young brilliant cylinder 4 place suitable for reading takes the lead in away from heating member 6 and becomes Wen Chang cold-zone, solid-liquid interface also shifts to cold-zone with the speed of 1mm/h from the hot-zone of warm field simultaneously, by the mass transport in melt, in crucible 3, the complete direction intrinsic according to seed crystal 13 constantly grows down by the crystal of growth, after 200 hours, crystal growth is complete, automatic cooling is controlled by temperature-control heat couple 10, cooling rate is 30 DEG C/h, temperature stops powering for heating member 6 when being down to 150 DEG C, naturally cool to room temperature, obtain the complete magnesium fluoride monocrystalline consistent with seed crystal 13 direction, ingot diameters 58mm, length 160mm, crystal ingot cylinder axis and crystal C are to parallel.Described fluoride single crystal also comprises CaF
2, BaF
2, LiF crystal.
Claims (4)
1. a device for little gradient temperature field rising oriented growth fluoride single crystal, be muff (2) in vacuum chamber (1) inner peripheral, crucible (3) is positioned at muff (2) center of inside; Have young brilliant cylinder (4) in crucible (3) bottom centre, young brilliant cylinder (4) is crucible holder (5) below; Several heating members (6) are contour is suspended on crucible (3) lateral wall circumference, heating member (6) upper end connects water cooled electrode bar (7), and battery lead rod (7) is first connected with electrode holder (9) through the sealing-ring (8) at vacuum chamber (1) top through muff (2) top again; Temperature-control heat couple (10) is positioned at the young brilliant cylinder At The Height in young brilliant cylinder (4) side 1/2 ~ 2/3; It is characterized in that, crucible (3) is placed in above muff (2) bottom through crucible holder (5); Electrode holder facing each other (9) couples together by each tie-beam (11), the mid point of each tie-beam (11) intersects at a point, each tie-beam (11) is connected to each other integral at this point, and the lower end of lifting rod (12) is connected with each tie-beam (11) at this point; Battery lead rod (7) coordinates with sealing-ring (8) is dynamic.
2. the device of little gradient temperature field rising oriented growth fluoride single crystal according to claim 1, is characterized in that, tie-beam (11) and electrode holder (9) insulate, supply lead receiving electrode seat (9).
3. the method for one kind little gradient temperature field rising oriented growth fluoride single crystal, son brilliant (13) is inserted young brilliant cylinder (4), the upper end of young brilliant (13) probes into crucible (3), growth material (14) is loaded crucible (3), the warm field of growth is produced by heating member (6), controlling warm field temperature residing for young brilliant (13) first half by temperature-control heat couple (10) is the temperature higher than grown fluoride single crystal fusing point 5 ~ 10 DEG C, after young brilliant (13) first half melts, young brilliant (13) and the upper and lower relative movement in warm field, solid-liquid interface shifts to cold-zone from the hot-zone of warm field, until crystal growth is complete, it is characterized in that, several heating members (6) are contour is suspended on crucible (3) lateral wall circumference, heating member (6) is upwards lifted by tie-beam (11), electrode holder (9), battery lead rod (7) by lifting rod (12), rise in temperature field thereupon, crucible (3), young brilliant cylinder (4), crucible holder (5), young brilliant (13) are static.
4. the method for little gradient temperature field rising oriented growth fluoride single crystal according to claim 3, it is characterized in that, upwards lift heating member (6) by tie-beam (11), electrode holder (9), battery lead rod (7) with the speed of 1 ~ 3mm/h by lifting rod (12).
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| CN105133005B (en) * | 2014-06-03 | 2018-01-09 | 长春理工大学 | Obtain the growing method and device of smooth solid liquid interface |
| CN104790025A (en) * | 2015-04-14 | 2015-07-22 | 营口市荣兴达科技实业有限公司 | Preparation device and preparation technology for magnesium fluoride single crystal coating material |
| CN105112993B (en) * | 2015-10-12 | 2017-10-20 | 山东大学 | A kind of device and method for adjusting micro- drop-down crystal growth thermal gradient |
| CN107287657B (en) * | 2017-06-26 | 2019-10-08 | 北京中材人工晶体研究院有限公司 | A kind of growing method and gained crystal of lanthanum bromide scintillation crystal |
| CN108866619A (en) * | 2018-07-02 | 2018-11-23 | 南京光宝光电科技有限公司 | The oriented growth device and technique of large scale magnesium fluoride monocrystalline |
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| CN1485467A (en) * | 2003-08-08 | 2004-03-31 | 中国科学院上海光学精密机械研究所 | Growth apparatus for large-areaed crystal by temperature gradient technique and crystal growth method thereof |
| CN1603475A (en) * | 2004-09-06 | 2005-04-06 | 周永宗 | Pure static state double heating apparatus for crystal growth by temperature gradient technique |
| CN102766901A (en) * | 2012-08-20 | 2012-11-07 | 元亮科技有限公司 | Device for growing large-size and high-temperature crystals with real-time adjustable temperature gradient method and method |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN1485467A (en) * | 2003-08-08 | 2004-03-31 | 中国科学院上海光学精密机械研究所 | Growth apparatus for large-areaed crystal by temperature gradient technique and crystal growth method thereof |
| CN1603475A (en) * | 2004-09-06 | 2005-04-06 | 周永宗 | Pure static state double heating apparatus for crystal growth by temperature gradient technique |
| CN102766901A (en) * | 2012-08-20 | 2012-11-07 | 元亮科技有限公司 | Device for growing large-size and high-temperature crystals with real-time adjustable temperature gradient method and method |
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Effective date of registration: 20160812 Address after: Three, Huaian 223001 Industrial Zone, Huaian District, Jiangsu Patentee after: HUAIAN HONGXIANG OPTOELECTRONIC TECHNOLOGY CO., LTD. Address before: 130022 No. 7989 Satellite Road, Changchun, Jilin, Chaoyang District Patentee before: changchun university of science and technology |
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Address after: 223001 Xingping Street, Pingqiao Town, Huaian District, Huaian City, Jiangsu Province Patentee after: Jiangsu Bridgeman Technology Co., Ltd Address before: Three, Huaian 223001 Industrial Zone, Huaian District, Jiangsu Patentee before: HUAIAN HONGXIANG GUANGDIAN TECHNOLOGY Co.,Ltd. |
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