CN103668455B - The grower of a kind of lbo crystal and growing method - Google Patents
The grower of a kind of lbo crystal and growing method Download PDFInfo
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- CN103668455B CN103668455B CN201210343210.1A CN201210343210A CN103668455B CN 103668455 B CN103668455 B CN 103668455B CN 201210343210 A CN201210343210 A CN 201210343210A CN 103668455 B CN103668455 B CN 103668455B
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Abstract
The present invention relates to the grower of a kind of lbo crystal, including the protuberance arranged on crucible and the bottom in described crucible.The invention still further relates to the growing method of a kind of lbo crystal, use described grower to carry out the growth of lbo crystal.The growth cell configuration that the present invention provides is simple, it is easy to manufacture, cost is relatively low；Grower and growing method that the present invention provides can go out heavy caliber flat LBO monocrystal with direct growth, reduce quartz crystal device cutting difficulty, significantly improve the utilization rate of crystal, decrease processing link, shorten crystal growth cycles, reduce manufacturing cost.
Description
Technical field
The present invention relates to crystal preparation field, be specifically related to a kind of grower for growing three Lithium biborates (LBO) crystal and corresponding growing method.
Background technology
Three Lithium biborate (LiB3O5, it being called for short LBO) and monocrystal is a kind of excellent nonlinear optical material.It has sufficiently large nonlinear factor, is at room temperature capable of phase matched, and deliquescence, stable chemical performance, hardness is not moderate, especially allows that angle, wide transparency range are good in other nonlinear crystals with its bigger laser damage threshold and phase matched.It is widely used among Solid State Laser frequency conversion field at present.
LBO is the compound of non-congruent melting, and its growth is main uses pyrosol top-seeded solution growth, top seeded solvent growth, crucible rotation method etc..
Technological break-through along with the growth of large scale lbo crystal, large scale lbo crystal device presents good application prospect as frequency conversion material in fields such as laser-produced fusion igniting, superpower ultrafast laser OPCPA, and the lbo crystal device that these new opplication require has the feature that the big thickness of bore is moderate.But the large scale lbo crystal of growth all presents the inverted cone that upper surface is big at present, the especially thickness around upper surface is both less than 5mm, cutting for lbo crystal device that thickness is 10mm, the utilization rate of lbo crystal is the lowest, if considering further that the cutting angle of different LBO requirement on devices is the most different, also can there is inclination angle in upper surface during cutting, then large scale lbo crystal is the lowest to the utilization rate of large aperture LBO device, thus cause cost high, the problems such as difficulty is big.
Summary of the invention
For overcoming the defect being difficult to prepare heavy caliber lbo crystal, crystal utilization rate is the highest in prior art, the present invention is directed to the demand of specific direction heavy caliber lbo crystal device, existing crystal growing apparatus is improved, it is therefore an objective to the grower of a kind of lbo crystal is provided.
It is a further object of the present invention to provide the growing method of a kind of lbo crystal.
The lbo crystal grower that the present invention provides, including the protuberance arranged on crucible and the bottom in described crucible.
Preferably, described protuberance is fixed on the bottom in described crucible by fixed forms such as welding.
Preferably, described protuberance top closure.The top of described protuberance can be most advanced and sophisticated, it is also possible to for plane, preferably plane.
The principle of above-mentioned crystal growing apparatus is: arrange protuberance in conventional crucible, is equivalent to suitably raise crucible bottom, suppresses, retrains the crystal growth at vertical direction；And the space around protuberance can accommodate more crystal growth raw material, sufficient raw material can make crystal then carry out cross growth after stopping vertically growth, and the crystal so obtained will not form the inverted cone of routine, and forms bigbore flat.
The height of described protuberance is determined by the degree of depth of crystal thickness to be grown and crucible；Described protuberance can have any shape, for example, it is possible to be the cylinder of rule, cone, square, cuboid etc.；It can also be the irregular modification structures of cylinder, cone, square, cuboid etc.；Can also be the structure of combination in any, the laminated structure such as arbitrary shape be fixed on crucible bottom protuberance forming similar umbrella etc. by fixing bar.Described protuberance can be arbitrary size, the topside area of protuberance is the biggest, suppression and binding effect to crystal growth are the best, but, when protuberance topside area is excessive, around cannot accommodate more raw material melt, manufacturing cost the most costly, therefore considers from cost-effective and the more raw material melts of receiving factors, and the topside area of protuberance is difficult to excessive, preferably, the topside area of protuberance is the 1/5～1/2 of crucible bottom area.
Preferably, described protuberance is regular or irregular column or is regular or irregular taper.
Preferably, the cross section of described protuberance is circular, oval or arbitrary polygon.
Preferably, described protuberance can be hollow-core construction or solid construction.
The growing method of the lbo crystal that the present invention provides, for flux method for growth, uses the grower described in above any one of technical scheme to carry out crystal growth.
Preferably, described growing method comprises the following steps:
(1) preparation is in order to the LBO raw material of crystal growth, is placed in grower described in above any one of technical scheme, is warming up to described raw material and is completely melt to obtain melt；
(2) introducing seed crystal, cooling starts to grow crystal；
(3), after crystal growth terminates, it is drawn off being down to room temperature and get final product.
Preferably, described crystal growth raw material is Li2CO3、H3BO3、MOO3With metal fluoride MF2(M is Be, Mg, Ca, Sr, Ba, Ra, Zn or Pb), described raw material uses the mol ratio of conventional crystalline growth raw material.
Described seed crystal direction can be any direction.
Preferably, described step (2) is: step (1) gained melt is warming up to more than saturation point temperature 1～10 DEG C, introduces seed crystal to the surface of described melt or wherein, after be incubated 1～20 hour, starts to grow crystal with the speed cooling of 0.05～1.50 DEG C/day.
In described step (2), it is additionally included in growth crystallization process the speed rotation seed crystal with 20～60rpm.
Described seed crystal rotate to be single direction rotation or bidirectional rotation；The seed rod that is rotated through of described seed crystal rotarily drives.
Described bidirectional rotation preferably rotates according to following swing circle: after accelerating the most successively to rotate, at the uniform velocity rotating, be rotated in deceleration and stop the rotation, then accelerate the most successively to rotate, at the uniform velocity rotate, be rotated in deceleration and stop the rotation.Acceleration during bidirectional rotation, deceleration, direction transformation etc. use routine techniques, and the present invention is not particularly limited.
Technical solution of the present invention has the advantages that
1) the invention provides a kind of novel crystal growing apparatus, simple in construction, simple for production, it is not necessary to too many material, with low cost, use this device can grow bigbore flat lbo crystal according to certain thickness.
2) grower that the present invention provides is by adjusting topside area and the height size of protuberance in crucible, the growth thickness of lbo crystal can be controlled as required, achieve the controllability of crystal shape, but also can substantially reduce the gross weight of growing LBO crystal, effectively reduce the risk come off because of the overweight LBO caused.
3) present invention provides grower and growing method can go out required heavy caliber flat LBO monocrystal with direct growth, LBO device can be cut out with parallel lbo crystal, reduce device cutting difficulty, significantly improve the utilization rate of crystal, decrease processing link, shorten crystal growth cycles, hence it is evident that reduce manufacturing cost.
Accompanying drawing explanation
Fig. 1 is the structural representation of lbo crystal grower described in the embodiment of the present invention 1；
In figure: 1, crucible；2, protuberance.
Detailed description of the invention
Following example are used for illustrating the present invention, but are not limited to the scope of the present invention.
Embodiment 1
As it is shown in figure 1, the crucible that crystal growing apparatus main body is upper end open, bottom lock of the present embodiment, the bottom in crucible being provided with a protuberance, described protuberance is the structure of top closure, is fixed on the bottom of crucible by modes such as welding.
As optional technical scheme, described protuberance can be the arbitrary structures of top closure, and its top can be the tip closed, it is also possible to for the plane of arbitrary shape.
As optional technical scheme, described protuberance can have any shape, and such as regular or irregular column, taper etc., its cross section can be circular, oval, square and arbitrary polygon etc.；Described protuberance can also be the structure of combination in any, forms the structure etc. of similar umbrella as the laminated structure of arbitrary shape is fixed on crucible bottom by fixing bar.
As optional technical scheme, described protuberance can be solid construction, it is also possible to for hollow-core construction.
When using the crystal growing apparatus growing LBO crystal of the present embodiment, process is as follows: first prepare powder body LBO growth raw material, is ground and mix homogeneously by highly purified material powder；Again mixed material powder is placed in crucible, is heated to high temperature and makes material powder be completely melt to form melt；Then to described bath surface or wherein introduce seed crystal, after insulation appropriate time, with specific cooling rate slow cooling, crystal growth began；Crystal is grown into downwards, until touching the protuberance top of crucible bottom, owing to crystal is obligated effect by protuberance top, crystal stops at the growth of vertical direction, simultaneously as protuberance surrounding space contains the raw material melt of abundance, therefore crystal is after stopping vertical direction growth, start cross growth, thus obtain the lbo crystal of heavy caliber flat.
Embodiment 2
By 947.04 grams of Li of analytical pure rank2CO3, 1584.58 grams of H3BO3, 1230.04 grams of MOO3With 441.72 grams of ZnF2Grinding in Achates dismembyator, uniformly load in crystal growing apparatus after mixing, the outside platinum crucible of grower is a size ofInternal nib be a cylinder (a size of).Aforementioned growth device is put in vertical resistance wire monocrystal growing furnace, the lid made of insulation material seals up furnace roof opening, between in the lid, corresponding crucible center stays one to be available for the aperture that seed rod comes in and goes out, it is heated to 900 DEG C with the heating rate of 80 DEG C/about h, the agitator made of platinum sheet stirs 12 hours at such a temperature, propose agitator, progressively cool to 660 DEG C.Enter to attempt down seed crystal and seek saturation point temperature accurately.Then entering formal seed crystal at above about 2-5 DEG C of saturation point temperature to bath surface, constant temperature, after 1 hour, starts slow cooling, is down to crystal growth began during saturation point temperature.Seed rod is carried out single direction rotation, and speed is 20rpm per minute, and rate of temperature fall is every day 0.05～0.8 DEG C.Terminating through 72 days crystal growth, at 20mm on crystal lift-off bath surface, be slow cooling to room temperature with the speed of about per hour 10 DEG C, finally obtaining size is 123 × 120 × 22mm3LBO monocrystalline.
Embodiment 3
By 1415.78 grams of Li of analytical pure rank2CO3, 1780.13 grams of H3BO3, 2763.65 grams of MOO3With 992.45 grams of ZnF2Grinding in Achates dismembyator, uniformly load in crystal growing apparatus after mixing, the outer crucible of grower is a size ofProtuberance in crucible is positive round cone (a size of base diameter 90mm, top diameter 70mm, a height of 100mm).Above-mentioned grower is put in vertical resistance wire monocrystal growing furnace, the lid made of insulation material seals up furnace roof opening, between in the lid, corresponding crucible center stays one to be available for the aperture that seed rod comes in and goes out, it is heated to 1000 DEG C with the heating rate of 60 DEG C/about h, after making above-mentioned crucible material be completely melt, the agitator using platinum sheet to manufacture stirs 48 hours at such a temperature, after crucible material stirs, agitator is proposed, progressively cool to 680 DEG C, enter to attempt down seed crystal and seek saturation point temperature accurately, then at above about 2-5 DEG C of saturation point temperature, formal seed crystal is entered at about 5cm below bath surface, after constant temperature 3 hours, start cooling, it is down to crystal growth began during saturation point temperature.Seed rod is carried out single direction rotation, and speed is about 35 turns per minute, and rate of temperature fall is 0.1～1 DEG C/day.Terminating through 105 days crystal growth, at 20mm on crystal lift-off bath surface, be slow cooling to room temperature with the speed of per hour 10 DEG C, finally obtaining size is 170 × 160 × 15mm3LBO monocrystalline.
Embodiment 4
By 797.91 grams of Li of analytical pure rank2CO3, 1001.32 grams of H3BO3, 2331.83 grams of MOO3With 473.42 grams of BaF2Grinding in Achates dismembyator, uniformly load in crystal growing apparatus after mixing, the outer crucible of grower is a size ofProtuberance within crucible is inverted cone (a size of base diameter 40mm, top diameter 60mm, a height of 80mm).Above-mentioned grower is put in vertical resistance wire monocrystal growing furnace, the lid made of insulation material seals up furnace roof opening, between in the lid, corresponding crucible center stays one to be available for the aperture that seed rod comes in and goes out, it is heated to 1050 DEG C with the heating rate of 30 DEG C/about h, after making above-mentioned crucible material be completely melt, the agitator made of platinum sheet stirs 72 hours at such a temperature, after crucible material stirs, agitator is proposed, progressively cool to 720 DEG C, enter to attempt down seed crystal and seek saturation point temperature accurately, then at above about 2-10 DEG C of saturation point temperature, formal seed crystal is entered to bath surface, after constant temperature 5 hours, cooling, it is down to crystal growth began during saturation point temperature.Seed rod is carried out bidirectional rotation, and the speed of rotation is 60 turns per minute, and timing conversion direction of rotation, rate of temperature fall is every day 0.2～1.5 DEG C.Terminating through 76 days crystal growth, at 30mm on crystal lift-off melt, be slow cooling to room temperature with the speed of per hour 40 DEG C, finally obtaining size is 137 × 122 × 18mm3LBO monocrystalline.
Embodiment 5
By 2170.35 grams of Li of analytical pure rank2CO3, 2178.8 grams of H3BO3, 5073.86 grams of MOO3With 2060.13 grams of BaF2Grinding in Achates dismembyator, uniformly load in crystal growing apparatus after mixing, the outer crucible of grower is a size ofInternal nib is the combinative structure of round bar welded top disk (a size of rod diameter 10mm, top disk diameter 100mm, a height of 110mm).Above-mentioned grower is put in vertical resistance wire monocrystal growing furnace, the lid made of insulation material seals up furnace roof opening, between in the lid, corresponding crucible center stays one to be available for the aperture that seed rod comes in and goes out, it is heated to 950 DEG C with the heating rate of 30 DEG C/about h, after making above-mentioned crucible material be completely melt, the agitator made of platinum sheet stirs 72 hours at such a temperature, after crucible material is full and uniform, agitator is proposed, progressively cool to about 751 DEG C, enter to attempt down seed crystal and seek saturation point temperature accurately.After constant temperature 20 hours, then entering formal seed crystal under above about 2-5 DEG C of saturation point to bath surface, constant temperature, after 2 hours, starts cooling, is down to crystal growth began during saturation point temperature.Seed rod is carried out single direction rotation, and speed is about 40 turns per minute, and rate of temperature fall is every day 0.05～0.6 DEG C.Terminate through 136 days crystal growth, at 10mm on crystal lift-off bath surface, be slow cooling to room temperature with the speed of per hour 15 DEG C, finally obtain size and be about 233 × 196 × 17mm3LBO monocrystalline.
Embodiment 6
By 886.56 grams of Li of analytical pure rank2CO3, 1112.58 grams of H3BO3, 1727.28 grams of MOO3With 882.72 grams of PbF2Grinding in Achates dismembyator, uniformly load in crystal growing apparatus after mixing, the outer crucible of grower is a size ofProtuberance in crucible is cube structure (size 90mm × 90mm × 90mm).Above-mentioned grower is put in vertical resistance wire monocrystal growing furnace, the lid made of insulation material seals up furnace roof opening, between in the lid, corresponding crucible center stays one to be available for the aperture that seed rod comes in and goes out, it is heated to 1020 DEG C with the heating rate of 80 DEG C/about h, after making above-mentioned crucible material be completely melt, the agitator made of platinum sheet stirs 12 hours at such a temperature, after crucible material is full and uniform, agitator is proposed, progressively cool to 690 DEG C, enter to attempt down seed crystal and seek saturation point temperature accurately.After constant temperature 10 hours, then entering formal seed crystal under above about 2-5 DEG C of saturation point to bath surface, constant temperature, after 6 hours, starts cooling, is down to crystal growth began during saturation point temperature.Seed rod is carried out single direction rotation, and the speed of rotation is about 20 turns per minute, and rate of temperature fall is every day 0.1～1.5 DEG C.Terminate through 68 days crystal growth, at 25mm on crystal lift-off melt, be slow cooling to room temperature with the speed of per hour 30 DEG C, finally obtain size and be about 134 × 118 × 11mm3LBO monocrystalline.
Although, the present invention is described in detail the most with a general description of the specific embodiments, but on the basis of the present invention, can make some modifications or improvements it, and this will be apparent to those skilled in the art.Therefore, these modifications or improvements without departing from theon the basis of the spirit of the present invention, belong to the scope of protection of present invention.
Claims (8)
1. a growing method for lbo crystal, for flux method for growth, it is characterised in that use a kind of lbo crystal grower to carry out crystal growth；Described lbo crystal grower includes the protuberance arranged on crucible and the bottom in described crucible；Described growth comprises the following steps:
(1) preparation is in order to the LBO raw material of crystal growth, is placed in described grower, is warming up to described raw material and is completely melt to obtain melt；
(2) introducing seed crystal, cooling starts to grow crystal；
(3), after crystal growth terminates, it is drawn off being down to room temperature and get final product；
Described step (2) is: step (1) gained melt is warming up to more than saturation point temperature 1～10 DEG C, introduce seed crystal to the surface or wherein of described melt, after being incubated 1～20 hour, lower the temperature with the speed of 0.05～1.50 DEG C/day and start to grow crystal.
Growing method the most according to claim 1, it is characterised in that the protuberance top closure of described lbo crystal grower.
Growing method the most according to claim 1 and 2, it is characterised in that the protuberance of described lbo crystal grower is regular or irregular column or is regular or irregular taper.
Growing method the most according to claim 3, it is characterised in that the cross section of the protuberance of described lbo crystal grower is circular, oval or arbitrary polygon.
5. according to the growing method described in any one of claim 1,2 or 4, it is characterised in that the protuberance of described lbo crystal grower is hollow-core construction or solid construction.
Growing method the most according to claim 3, it is characterised in that the protuberance of described lbo crystal grower is hollow-core construction or solid construction.
Growing method the most according to claim 1, it is characterised in that in described step (2), is additionally included in growth crystallization process the speed rotation seed crystal with 20～60rpm.
Growing method the most according to claim 7, it is characterised in that described seed crystal rotate to be single direction rotation or bidirectional rotation.
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| CN108546988B (en) * | 2018-04-27 | 2019-06-04 | 东莞市三嘉光学科技有限公司 | One kind being suitable for multispectral optical crystal material technology of preparing equipment |
| CN108385169B (en) * | 2018-04-27 | 2019-01-11 | 南通向阳光学元件有限公司 | A kind of optical crystal material technology of preparing equipment of special applications |
| CN113699592B (en) * | 2020-05-22 | 2023-07-07 | 天津理工大学 | Method for growing large-size LBO crystal with assistance of machine learning and application thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1422993A (en) * | 2001-11-30 | 2003-06-11 | 中国科学院福建物质结构研究所 | Growth of LiB3O5 nonlinear optical crystal by integrating rotary crucible and molten salt Czochralski growth method |
| CN101319348A (en) * | 2008-06-13 | 2008-12-10 | 青岛大学 | Inverse-conical dropped bottom type crystal growth apparatus |
| CN102146580A (en) * | 2011-03-21 | 2011-08-10 | 浙江碧晶科技有限公司 | Seeding mold for growing silicon crystals by using orientated solidification method and crystal growing method |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1422993A (en) * | 2001-11-30 | 2003-06-11 | 中国科学院福建物质结构研究所 | Growth of LiB3O5 nonlinear optical crystal by integrating rotary crucible and molten salt Czochralski growth method |
| CN101319348A (en) * | 2008-06-13 | 2008-12-10 | 青岛大学 | Inverse-conical dropped bottom type crystal growth apparatus |
| CN102146580A (en) * | 2011-03-21 | 2011-08-10 | 浙江碧晶科技有限公司 | Seeding mold for growing silicon crystals by using orientated solidification method and crystal growing method |
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