CN101942699A - Method for growing calcium borate oxysalt crystal with frequency multiplication effect - Google Patents
Method for growing calcium borate oxysalt crystal with frequency multiplication effect Download PDFInfo
- Publication number
- CN101942699A CN101942699A CN 201010272983 CN201010272983A CN101942699A CN 101942699 A CN101942699 A CN 101942699A CN 201010272983 CN201010272983 CN 201010272983 CN 201010272983 A CN201010272983 A CN 201010272983A CN 101942699 A CN101942699 A CN 101942699A
- Authority
- CN
- China
- Prior art keywords
- crystal
- lime borate
- growth
- oxonium salt
- polycrystal
- 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.)
- Pending
Links
Abstract
The invention relates to a method for growing a calcium borate oxysalt crystal with a frequency multiplication effect. The method comprises the following steps of: weighing raw materials according to a stoichiometric ratio of a chemical equation of the calcium borate oxysalt and performing crystal growth by the traditional pulling method, wherein a seed crystal is formed by finding the direction of the maximum nonlinear coefficient of the calcium borate oxysalt crystal which grows in the traditional direction through X-ray diffraction and cutting the crystal along the optimum phase matching direction; conveying the cut seed crystal slowly, vertically and downwards into polycrystal material melt to make the top of the seed crystal contact with the polycrystal material melt; maintaining the seed crystal to grow in the vertical direction of the polycrystal material liquid level of the calcium borate oxysalt; and obtaining the calcium borate oxysalt crystal with the frequency multiplication effect through three technological processes of necking, shouldering and ending. The method avoids the defects of complicated process, low utilization ratio, low properties of devices and the like caused by that the traditional calcium borate oxysalt crystal grows along the b direction. The method has the advantages of high optical homogeneity in the light-transmitting direction and high practical value.
Description
Technical field
The present invention relates to a kind of growing method, particularly relate to a kind of lime borate oxygen yttrium YCa with frequency-doubled effect with frequency-doubled effect
4O (BO
3)
3(below write a Chinese character in simplified form: YCOB) or lime borate oxygen gadolinium GdCa
4O (BO
3)
3, (write a Chinese character in simplified form: GdCOB], and from the neodymium Nd of frequency-doubled effect
3+The be complementary growth method of direction of doping YCOB or GdCOB crystal optimum bit.
Background technology
Frequency multiplication is as a kind of important frequency inverted means, be widely used in optical storage, Laser Printing, laser indication, deep-sea detecting and communicate by letter, military commanding etc. and be related to the field of the international people's livelihood, and showed important application prospects in fields such as laser displaies.As a kind of important double-frequency material, lime borate oxygen yttrium YCa
4O (BO
3)
3(below write a Chinese character in simplified form: YCOB) or lime borate oxygen gadolinium Ca
4O (BO
3)
3, (write a Chinese character in simplified form: GdCOB] since its invention, just be subjected to people's extensive concern, and with realized the laser output of frequency multiplication and frequency tripling as frequency-changer cyrstal.Such material belongs to oblique system, has that nonlinear factor is big, optic damage threshold value is high, sees through advantages such as wide waveband, available Czochralski grown.In addition, (as Nd, Yb) after the doping, such material still is a kind of good self-frequency doubling laser crystal, has had the characteristic of laser and frequency conversion simultaneously, has realized multi-functional compound and miniaturization of devices, meets the development trend of functional materials to carry out ion.
(Re=Y Gd) belongs to oblique system, Cm spacer, and the size of its effective nonlinear coefficient is along with the crystal optical direction changes for doping or pure ReCOB.Theoretical Calculation and experiment showed, that the phase matched direction of its maximum effective nonlinear coefficient is not to be positioned at principal plane, but be positioned at the 5th octant (180 °＞θ＞90 °, 90 °＞φ＞0 °).And after mixing, the direction of its maximum effective nonlinear coefficient is unaffected substantially, and best crystal-cut direction does not change substantially yet.
The growth of this serial crystal at present generally all adopts crystalline b direction to grow, and determines the best from the frequency multiplication direction by orientation in actual applications, is processed into afterwards along the quartz crystal device of best frequency multiplication (comprising from frequency multiplication) direction.Such growth pattern has brought following shortcoming to crystalline processing, utilization and final devices:
(1) processed complex: the crystal of at every turn growing all will carry out orientation by X ray, determines optimum orientation afterwards, and this has just brought great difficulty to crystal processing virtually, makes the quality of quartz crystal device be decided by the accuracy of machine direction.
(2) utilization ratio is low: crystal overall dimension be positioned at its direction of growth b to, and after crystal carries out orientation, find plane perpendicular to best frequency multiplication direction, cut along best frequency multiplication direction afterwards, this makes and is difficult to obtain maximum sized processed sample that utilization ratio is lower.
(3) device performance is poor: bulk-growth is method of crystal growth by crystal pulling particularly, be to force crystal is grown along specific direction, in process of growth, because the interference of ambient conditionss such as temperature fluctuation, can form defectives such as striation perpendicular to the direction of growth in the edge, therefore along the crystal of direction of growth cutting, its optical homogeneity is best.And in actually operating, to growth, the optimum bit direction that is complementary has an angle to crystal with it, make its optical homogeneity be difficult to be guaranteed, and has influenced the performance and the application of resulting devices along b.
In sum, because the selection of the conventional crystal direction of growth, brought processed complex, utilization ratio is low and each side problem such as device performance difference, and unique solution route is exactly to grow along the crystalline optimum bit direction that is complementary.
Summary of the invention
The objective of the invention is to: at existing rare earth Nd
3+Mix or pure lime borate oxygen yttrium YCOB or lime borate oxygen gadolinium GdCOB because symmetry is low, the optimum phase matching direction is in principal plane, shortcomings such as the low and device performance difference of crystal processed complex, the utilization ratio of bringing, thereby provide a kind of be complementary seed crystal of direction cutting of optimum bit that uses, the growth method that adopts traditional crystal pulling method to carry out the crystal growth of lime borate oxonium salt, this method have solved the processed complex that conventional growth method is brought, utilization ratio is low and problem such as device performance difference.
The objective of the invention is such realization:
Lime borate oxonium salt crystalline growth method with frequency-doubled effect provided by the invention adopts crystal pulling method, may further comprise the steps:
1). the stoichiometric ratio according to the chemical equation of lime borate oxonium salt takes by weighing raw material;
Wherein, described lime borate oxonium salt comprises:
Lime borate oxygen yttrium YCa
4O (BO
3)
3
Lime borate oxygen gadolinium GdCa
4O (BO
3)
3Or
Neodymium-doped (Nd
3+) lime borate oxygen yttrium Nd
xY
1-xCa
4O (BO
3)
3, (below write a Chinese character in simplified form: Nd:YCOB);
Neodymium-doped (Nd
3+) lime borate oxygen gadolinium Nd
xGd
1-xCa
4O (BO
3)
3, (write a Chinese character in simplified form: Nd:GdCOB) wherein, Nd
3+Doping content x is 0.001-0.25at.;
2). step 1) is taken by weighing raw material mix, and put people's platinum crucible behind the mould briquetting of packing into, carry out sintering, sintering temperature 1000-1400 ℃, obtain lime borate oxonium salt polycrystal; Crucible carries out sintering, sintering temperature 1000-1400 ℃, obtains lime borate oxonium salt polycrystal;
3) step 2) polycrystal of the lime borate oxonium salt that obtains puts into Iridium Crucible, and charged Iridium Crucible is put into single crystal growing furnace vacuumize, and shielding gas nitrogen is gone in inflation; Adopt the mode of heating in medium frequency, be warmed up to the polycrystal fusing, be cooled to condense (it is following to be cooled to 1600 degree usually) afterwards, it is condensed, the polycrystal that is warming up to the lime borate oxonium salt afterwards melts, repeatedly at least twice, thereby bubble is Removed All, overheated 20-50 ℃, constant temperature 0.5-3 hour, raw material is mixed as far as possible, the lime borate oxonium salt polycrystal liquation that obtains melting;
4) the lime borate oxonium salt crystal that a usual way is grown, find out the direction of this lime borate oxonium salt crystal nonlinear factor maximum by the X-ray diffraction technology, and, be optimum bit and be complementary crystal that direction cuts out as seed crystal along the crystal that the direction of this lime borate oxonium salt crystal nonlinear factor maximum cuts out;
5) with step 4) with optimum bit be complementary that direction cuts seed crystal send in the single crystal growing furnace.And slowly deliver to vertically downward in the polycrystal liquation that step 3) obtains, the top of seed crystal is contacted with the polycrystal liquation get final product; And keep seed crystal to grow perpendicular to the direction of polycrystal liquid level, be along the optimum bit direction growth that is complementary; Afterwards by receiving neck, shouldering, three technological processs of ending;
Wherein, when receiving neck, pull rate comparatively fast is 2-10mm/ hour, and when the seed crystal radius was received to 1～1.5mm, beginning was with 0.5-20 degree/hour slowly cooling; Carry out shouldering again, pull rate was reduced to 0.5～2mm/ hour; When the diameter of crystal shoulder reaches the 20-40mm left and right sides, again with the 0.5-10 degree/hour speed heat up, carry out isodiametric growth, the normal growth of this moment is that pull rate is 0.5-2mm/ hour, rotating speed is 10～30 rev/mins; Prepare to carry to take off crystal when pulling crystal to diameter is about the 20-50 millimeter, its concrete operations of putting forward the process of taking off are as follows:
With 20-50 degree/hour slow elevated temperature, treat temperature rising 1-10 degree, the crystal bottom of lime borate oxonium salt is the time receiving inwardly, pulling rate was increased to 5-20mm/ hour, crystal and liquation are broken away from, set cooling process then and reduce to room temperature, rate of temperature fall be the 20-50 degree/hour; The whole temperature-fall period time is longer, is approximately 2-5 days, obtains along the be complementary lime borate oxonium salt crystal of direction growth of optimum bit; Slowly cooling can be carried out crystalline annealing simultaneously, and the thermal stresses that produces when discharging crystal growth keeps perfection of crystal, can avoid the crystal cleavage that causes owing to thermal stresses.
In the above-mentioned technical scheme, carrying out crystal pulling method when growing, for guaranteeing to contain the growth of oxygen crystalline, need be added with a spot of oxygen in protective atmosphere, its oxygen content is the 1-5% of volume.
In above-mentioned steps 5) isometrical process in, the pull rate of preferred crystal growth is 0.5～2 millimeter/hour, 10～30 rev/mins of rotating speeds.
In above-mentioned technical scheme, the cut direction of described seed crystal (being frequency multiplication (comprising from frequency multiplication) crystalline frequency multiplication phase matched direction) is:
For Nd:YCOB or YCOB crystal, the direction of growth is: θ=113 ° ± 5 °, φ=36.5 ° ± 5 °; Or θ=67 ° ± 5 °, φ=143 ° ± 5 °;
For Nd:GdCOB or GdCOB crystal, the direction of growth is: θ=113 ° ± 5 °, φ=47.5 ° ± 5 °; Or θ=67 ° ± 5 °, φ=132.5 ° ± 5 °.
In above-mentioned technical scheme, described seed crystal is shaped as rectangular parallelepiped, right cylinder or arbitrary shape.
In above-mentioned technical scheme, comprise also that crystal after coming out of the stove is placed in the resistance furnace to anneal that annealing temperature is 900-1200 ℃, annealing time is 5-12 hour.
A kind of along the optimum bit direction growth rare earth Nd that is complementary
3+Mix or pure lime borate oxygen yttrium YCOB or the growth method of lime borate oxygen gadolinium GdCOB, comprised direction growth, the borate doped calcium oxygen of Nd gadolinium GdCOB crystalline optimum bit direction growth, lime borate oxygen yttrium YCOB crystalline optimum bit direction growth, the lime borate oxygen gadolinium GdCOB crystalline optimum bit direction growth that is complementary that is complementary that is complementary that is complementary of the borate doped calcium oxygen of Nd yttrium YCOB crystalline optimum bit.Above-mentioned serial crystal can be grown with seed crystal, the traditional crystal pulling method of employing of the direction that is complementary along each self-alignment.
Lime borate oxonium salt crystalline growth method with frequency-doubled effect provided by the invention, compare, have the following advantages with adopting traditional direction of growth (b to) lime borate oxonium salt crystalline method of growing:
(1) crystal processing is simple: because the present invention adopts and is complementary along lime borate oxonium salt crystal optimum bit that direction grows, so resulting lime borate oxonium salt crystal crystal, need not special orientation, as long as cut along crystal growth direction, can obtain the crystal of compound frequency multiplication (comprising) direction from frequency multiplication, having simplified crystal processing makes and helps need of industrial production by oriented program.
(2) crystal utilization ratio height: along the be complementary crystal of direction growth of optimum bit, need not optimum bit that the conventional crystal direction of growth brings the determining of direction that be complementary, and crystalline overall dimension is present in the optimum bit direction that is complementary, obtain the large-size crystals device easily, and the maximized crystalline utilization ratio that improved.
(3) improved the performance of quartz crystal device: the crystalline quality has determined the performance of quartz crystal device.Crystal along best frequency multiplication (comprising) the direction growth of crystal from frequency multiplication, it has best homogeneity on the direction of growth, therefore determined that the lime borate oxonium salt quartz crystal device of cutting has best homogeneity in the direction, can improve the quality and the performance of quartz crystal device greatly.
Embodiment
The present invention will be further described below in conjunction with embodiment.
Embodiment 1
Present embodiment preparation is along the lime borate oxonium salt Nd of best frequency multiplication direction (θ=113 ° ± 5 °, φ=36.5 ° ± 5 °) growth
0.1Y
0.9Ca
4O (BO
3)
3Wherein, the Nd doping content is x=0.1.
The high-purity Y of the employing of present embodiment
2O
3, Nd
2O
3, CaCO
3With boric acid be raw material, use conventional crystal pulling method, concrete steps are as follows:
1). the preparation lime borate oxonium salt crystalline method according to routine is calculated raw material: promptly by following lime borate oxonium salt Nd
xY
1-xCa
4O (BO
3)
3The stoichiometric ratio of crystal-chemical formula takes by weighing raw material, wherein, and Nd
3+Doping content x is 0.1; Be Nd
0.1Y
0.9Ca
4O (BO
3)
3Chemical equation is as follows:
0.1Nd
2O
3+ 0.9Y
2O
3+ 8CaCO
3+ 6H
3BO
3→ 2Nd
0.1Y
0.9Ca
4O (BO
3)
3+ 8CO
2↑+9H
2O ↑ raw material total amount is decided according to crucible size and demand, and present embodiment is about 500g;
2). step 1) is taken by weighing raw material mix, and put people's platinum crucible behind the mould briquetting of packing into, carry out sintering, 1200 ℃ of sintering temperatures obtain lime borate oxonium salt Nd
0.1Y
0.9Ca
4O (BO
3)
3Polycrystal;
3) step 2) Nd that obtains
0.1Y
0.9Ca
4O (BO
3)
3Polycrystal put into Iridium Crucible, charged Iridium Crucible is put into single crystal growing furnace vacuumizes, and charge into 2%O
2+ N
2Shielding gas; Adopt the mode of heating in medium frequency, be warmed up to 1650 ℃ and make Nd
0.1Y
0.9Ca
4O (BO
3)
3Polycrystal fusing, be cooled to condense (it is following to be cooled to 1600 degree usually) afterwards, it is condensed, and the polycrystal that is warming up to the lime borate oxonium salt afterwards melts repeated multiple times, for example twice, thereby bubble is Removed All, overheated 20-50 ℃, constant temperature 0.5-3 hour, raw material is mixed as far as possible, the lime borate oxonium salt polycrystal liquation that obtains melting;
4) get the lime borate oxonium salt crystal that a usual way is grown, find out the direction of this Nd:YCOB crystal nonlinear factor maximum by the X-ray diffraction technology, and, be optimum bit and be complementary crystal that direction cuts out as seed crystal along the crystal that the direction of this Nd:YCOB crystal nonlinear factor maximum cuts out; Be that seed crystal is that the Nd:YCOB crystalline size is 5mm * 5mm * 20mm along (θ=113 ° ± 5 °, φ=36.5 ° ± 5 °) the Nd:YCOB crystal that direction cuts out;
5) step 4) is sent in the single crystal growing furnace with the optimum bit seed crystal that direction cuts Nd:YCOB that is complementary.And slowly deliver to vertically downward in the polycrystal liquation that step 3) obtains, the top of seed crystal is contacted with the polycrystal liquation get final product; And keep seed crystal to grow perpendicular to the direction of polycrystal liquid level, be along the optimum bit direction growth that is complementary; Afterwards by receiving neck, shouldering, three technological processs of ending;
Wherein, when receiving neck, the pull rate of crystal growth is 0.5～2 millimeter/hour, 10～30 rev/mins of rotating speeds, and crystal growth temperature is between 1450-1650 ℃.Crystal growth finishes and is cooled to room temperature, and crystal is come out of the stove; The crystal of coming out of the stove is placed in the resistance furnace anneals, and annealing temperature is 1000 ℃, and annealing time is 8 hours, can partly discharge growth of Nd like this
0.1Y
0.9Ca
4O (BO
3)
3The thermal stresses that produces in the crystal process.The crystal that is obtained is along the be complementary lime borate oxonium salt Nd of direction (θ=113 ° ± 5 °, φ=36.5 ° ± 5 °) of optimum bit
0.1Y
0.9Ca
4O (BO
3)
3
Embodiment 2
Preparation is along the lime borate oxonium salt Nd of best frequency multiplication direction (θ=67 ° ± 5 °, φ=143 ° ± 5 °) growth
0.001Y
0.999Ca
4O (BO
3)
3Crystal (Nd:YCOB crystal); Wherein, the Nd doping content is x=0.001.
The growth technique of present embodiment is described with embodiment 1, and different is is (θ=67 ° ± 5 °, φ=143 ° ± 5 °) in the seed crystal cut direction.
1). according to Nd
0.001Y
0.999Ca
4O (BO
3)
3Stoichiometric ratio takes by weighing raw material, its chemical equation:
0.001Nd
2O
3+ 0.999Y
2O
3+ 8CaCO
3+ 6H
3BO
3→ 2Nd
0.001Y
0.999Ca
4O (BO
3)
3+ 8CO
2↑+9H
2O ↑ raw material total amount is decided according to crucible size and demand, and present embodiment is about 300g;
2). step 1) is taken by weighing raw material mix, and put people's platinum crucible behind the mould briquetting of packing into, carry out sintering, 1000 ℃ of sintering temperatures obtain lime borate oxonium salt Nd
0.001Y
0.999Ca
4O (BO
3)
3Polycrystal;
3) step 2) Nd that obtains
0.001Y
0.999Ca
4O (BO
3)
3Polycrystal put into Iridium Crucible, charged Iridium Crucible is put into single crystal growing furnace vacuumizes, and charge into 2%O
2+ N
2Shielding gas; Adopt the mode of heating in medium frequency, be warmed up to 1700 ℃ and make Nd
0.001Y
0.999Ca
4O (BO
3)
3Polycrystal fusing, be cooled to condense (it is following to be cooled to 1600 degree usually) afterwards, it is condensed, and the polycrystal that is warming up to the lime borate oxonium salt afterwards melts repeated multiple times, for example twice, thereby bubble is Removed All, overheated 50 ℃, constant temperature 0.5 hour, raw material is mixed as far as possible, the lime borate oxonium salt polycrystal liquation that obtains melting;
4) get the lime borate oxonium salt crystal that a usual way is grown, find out the direction of this Nd:YCOB crystal nonlinear factor maximum by the X-ray diffraction technology, and, be optimum bit and be complementary crystal that direction cuts out as seed crystal along the crystal that the direction of this Nd:YCOB crystal nonlinear factor maximum cuts out; Be that seed crystal is that the Nd:YCOB crystalline size is 5mm * 5mm * 30mm along (θ=67 ° ± 5 °, φ=143 ° ± 5 °) the Nd:YCOB crystal that direction cuts out;
5) step 4) is sent in the single crystal growing furnace with the optimum bit seed crystal that direction cuts Nd:YCOB that is complementary.And slowly deliver to vertically downward in the polycrystal liquation that step 3) obtains, the top of seed crystal is contacted with the polycrystal liquation get final product; And keep seed crystal to grow perpendicular to the direction of polycrystal liquid level, be along the optimum bit direction growth that is complementary; Afterwards by receiving neck, shouldering, three technological processs of ending;
Wherein, when receiving neck, the pull rate of crystal growth is 0.5～2 millimeter/hour, 10～30 rev/mins of rotating speeds, and crystal growth temperature is between 1450-1650 ℃.Crystal growth finishes and is cooled to room temperature, and crystal is come out of the stove; The crystal of coming out of the stove is placed in the resistance furnace anneals, and annealing temperature is 1200 ℃, and annealing time is 12 hours, can partly discharge growth of Nd like this
0.001Y
0.999Ca
4O (BO
3)
3The thermal stresses that produces in the crystal process.The crystal that is obtained is along the be complementary Nd of direction (θ=67 ° ± 5 °, φ=143 ° ± 5 °) of optimum bit
0.001Y
0.999Ca
4O (BO
3)
3Crystal.
Embodiment 3
Preparation is along best frequency multiplication direction (θ=113 ° ± 5 °, φ=36.5 ° ± 5 °) growth YCOB crystal.
As described in embodiment 1, different is that material choice is Y
2O
3, CaCO
3And boric acid, according to YCa
4O (BO
3)
3Chemical formula is prepared burden:
Y
2O
3+8CaCO
3+6H
3BO
3→2YCa
4O(BO
3)
3+8CO
2↑+9H
2O↑
Seed crystal is the Nd:YCOB crystal that cuts out along (θ=113 ° ± 5 °, φ=36.5 ° ± 5 °) direction,
Its process of growth is identical with embodiment 1.
Embodiment 4
Preparation is along the YCOB crystal of best frequency multiplication direction (θ=67 ° ± 5 °, φ=143 ° ± 5 °) growth.
Material choice and preparation thereof are shown in embodiment 3, and different is, and to select seed crystal for use be crystal along (θ=67 ° ± 5 °, φ=143 ° ± 5 °) direction cutting, obtain along the be complementary YCOB crystal of direction growth of optimum bit according to the process of growth of embodiment 2.
Embodiment 5
Preparation is along the Nd of best frequency multiplication direction (θ=113 ° ± 5 °, φ=47.5 ° ± 5 °) growth
xGd
1-xCa
4O (BO
3)
3Crystal, wherein, the Nd doping content is 0.15.
Concrete steps are as follows:
1) material choice is Gd
2O
3, Nd
2O
3, CaCO
3And boric acid, press the chemical equation body as seed crystal; Be that seed crystal is that the Nd:YCOB crystalline size is 5mm * 5mm * 30mm along (θ=67 ° ± 5 °, φ=143 ° ± 5 °) the Nd:YCOB crystal that direction cuts out;
5) step 4) is sent in the single crystal growing furnace with the optimum bit seed crystal that direction cuts Nd:YCOB that is complementary.And slowly deliver to vertically downward in the polycrystal liquation that step 3) obtains, the top of seed crystal is contacted with the polycrystal liquation get final product; And keep seed crystal to grow perpendicular to the direction of polycrystal liquid level, be along the optimum bit direction growth that is complementary; Afterwards by receiving neck, shouldering, three technological processs of ending;
Wherein, when receiving neck, the pull rate of crystal growth is 0.5～2 millimeter/hour, 10～30 rev/mins of rotating speeds, and crystal growth temperature is between 1450-1650 ℃.Crystal growth finishes and is cooled to room temperature, and crystal is come out of the stove; The crystal of coming out of the stove is placed in the resistance furnace anneals, and annealing temperature is 1200 ℃, and annealing time is 12 hours, can partly discharge growth of Nd like this
0.001Y
0.999Ca
4O (BO
3)
3The thermal stresses that produces in the crystal process.The crystal that is obtained is along the be complementary Nd of direction (θ=67 ° ± 5 °, φ=143 ° ± 5 °) of optimum bit
0.001Y
0.999Ca
4O (BO
3)
3Crystal.
Embodiment 3
Preparation is along best frequency multiplication direction (θ=113 ° ± 5 °, φ=36.5 ° ± 5 °) growth YCOB crystal.
As described in embodiment 1, different is that material choice is Y
2O
3, CaCO
3And boric acid, according to YCa
4O (BO
3)
3Chemical formula is prepared burden:
Y
2O
3+8CaCO
3+6H
3BO
3→2YCa
4O(BO
3)
3+8CO
2↑+9H
2O↑
Seed crystal is the Nd:YCOB crystal that cuts out along (θ=113 ° ± 5 °, φ=36.5 ° ± 5 °) direction,
Its process of growth is identical with embodiment 1.
Embodiment 4
Preparation is along the YCOB crystal of best frequency multiplication direction (θ=67 ° ± 5 °, φ=143 ° ± 5 °) growth.
Material choice and preparation thereof are shown in embodiment 3, and different is, and to select seed crystal for use be crystal along (θ=67 ° ± 5 °, φ=143 ° ± 5 °) direction cutting, obtain along the be complementary YCOB crystal of direction growth of optimum bit according to the process of growth of embodiment 2.
Embodiment 5
Preparation is along the Nd of best frequency multiplication direction (θ=113 ° ± 5 °, φ=47.5 ° ± 5 °) growth
xGd
1-xCa
4O (BO
3)
3Crystal, wherein, the Nd doping content is 0.15.
Concrete steps are as follows:
1) material choice is Gd
2O
3, Nd
2O
3, CaCO
3And boric acid, press chemical equation
0.15Nd
2O
3+ 0.85Gd
2O
3+ 8CaCO
3+ 6H
3BO
3→ 2Nd
0.15Gd
0.85Ca
4O (BO
3)
3+ 8CO
2↑+9H
2O ↑ take by weighing raw material.The raw material total amount is decided according to crucible size and demand, and present embodiment is about 400g;
2). step 1) is taken by weighing raw material mix, and put people's platinum crucible behind the mould briquetting of packing into, carry out sintering, 900 ℃ of sintering temperatures obtain lime borate oxonium salt Nd
0.15Gd
0.85Ca
4O (BO
3)
3Polycrystal;
3) step 2) Nd that obtains
0.15Gd
0.85Ca
4O (BO
3)
3Polycrystal put into Iridium Crucible, charged Iridium Crucible is put into single crystal growing furnace vacuumizes, and charge into 2%O
2+ N
2Shielding gas; Adopt the mode of heating in medium frequency, be warmed up to 1650 ℃ and make Nd
0.15Y
0.85Ca
4O (BO
3)
3Polycrystal fusing, be cooled to condense (it is following to be cooled to 1600 degree usually) afterwards, it is condensed, and the polycrystal that is warming up to the lime borate oxonium salt afterwards melts repeated multiple times, for example twice, thereby bubble is Removed All, overheated 20-50 ℃, constant temperature 1 hour, raw material is mixed as far as possible, the lime borate oxonium salt polycrystal liquation that obtains melting;
4) get the lime borate oxonium salt crystal that a usual way is grown, find out the direction of this Nd:GdCOB crystal nonlinear factor maximum by the X-ray diffraction technology, and, be optimum bit and be complementary crystal that direction cuts out as seed crystal along the crystal that the direction of this Nd:GdCOB crystal nonlinear factor maximum cuts out; Be that seed crystal is that the Nd:GdCOB crystalline size is 5mm * 5mm * 25mm along (θ=113 ° ± 5 °, φ=47.5 ° ± 5 °) the Nd:GdCOB crystal that direction cuts out;
5) step 4) is sent in the single crystal growing furnace with the optimum bit seed crystal that direction cuts Nd:GdCOB that is complementary.And slowly deliver to vertically downward in the polycrystal liquation that step 3) obtains, the top of seed crystal is contacted with the polycrystal liquation get final product; And keep seed crystal to grow perpendicular to the direction of polycrystal liquid level, be along the optimum bit direction growth that is complementary; Afterwards by receiving neck, shouldering, three technological processs of ending;
Wherein, when receiving neck, the pull rate of crystal growth is 0.5～2 millimeter/hour, 10～30 rev/mins of rotating speeds, and crystal growth temperature is between 1450-1650 ℃.Crystal growth finishes and is cooled to room temperature, and crystal is come out of the stove; The crystal of coming out of the stove is placed in the resistance furnace anneals, and annealing temperature is 1100 ℃, and annealing time is 8 hours, can partly discharge growth of Nd like this
0.15Gd
0.85Ca
4O (BO
3)
3The thermal stresses that produces in the crystal process.The crystal that is obtained is along optimum bit direction (the lime borate oxonium salt Nd of (θ=113 ° ± 5 °, φ=47.5 ° ± 5 °) that is complementary
0.15Gd
0.85Ca
4O (BO
3)
3
Embodiment 6
Preparation is along the Nd of best frequency multiplication direction (θ=67 ° ± 5 °, φ=132.5 ° ± 5 °) growth
0.15Gd
0.85Ca
4O (BO
3)
3Crystal, wherein, the Nd doping content is 0.25.
Shown in embodiment 5, seed crystal direction that different is is (θ=67 ° ± 5 °, φ=132.5 ° ± 5 °), and proportioning raw materials is according to chemical equation
0.25Nd
2O
3+ 0.75Gd
2O
3+ 8CaCO
3+ 6H
3BO
3→ 2Nd
0.25Gd
0.75Ca
4O (BO
3)
3+ 8CO
2↑+9H
2O ↑ employing seed crystal cut direction is (θ=67 ° ± 5 °, φ=132.5 ° ± 5 °), and process of growth obtains along the be complementary Nd of direction growth of optimum bit
0.15Gd
0.85Ca
4O (BO
3)
3Crystal.
Embodiment 7
Preparation is along the GdCOB crystal of best frequency multiplication direction (θ=113 ° ± 5 °, φ=47.5 ° ± 5 °) growth.
As described in embodiment 5, different is that material choice is Gd
2O
3, CaCO
3And boric acid,
Press chemical equation
Gd
2O
3+8CaCO
3+6H
3BO
3→2GdCa
4O(BO
3)
3+8CO
2↑+9H
2O↑
Its process of growth is identical with embodiment 5, and different is selects for use along the GdCOB seed crystal of (θ=113 ° ± 5 °, φ=47.5 ° ± 5 °) direction cutting.
Embodiment 8
Preparation is along the GdCOB crystal of best frequency multiplication direction (θ=67 ° ± 5 °, φ=132.5 ° ± 5 °) growth.
Shown in embodiment 7, the GdCOB seed crystal of direction cutting that different is selects for use (θ=67 ° ± 5 °, φ=132.5 ° ± 5 °) obtains along the be complementary GdCOB crystal of direction growth of optimum bit according to the process of growth of embodiment 5.
Growth method of the present invention selects for use optimum bit to be complementary the crystal of direction as seed crystal, adopts traditional crystal pulling method to grow, and obtains the be complementary crystal of direction of optimum bit.Shortcomings such as the low and device performance difference of processed complex, the utilization ratio of having brought when growth method of the present invention has avoided traditional lime borate oxonium salt crystal to select for use the b direction to carry out the direction of growth, have the orientation of need not, utilization ratio maximization and optical direction optical homogeneity advantages of higher, the demand that meets suitability for industrialized production has important practical value and application prospect.
Should be noted that; those of ordinary skills can understand the detailed description of above the present invention being carried out; and may make amendment to part technical characterictic of the present invention; and not breaking away from the connotation of technical solution of the present invention, these changes all should be encompassed among the technical scheme scope that the present invention asks for protection.
Claims (6)
1. the lime borate oxonium salt crystalline growth method with frequency-doubled effect adopts crystal pulling method, may further comprise the steps:
1). the stoichiometric ratio according to the chemical equation of lime borate oxonium salt takes by weighing raw material;
Wherein, described lime borate oxonium salt comprises:
Lime borate oxygen yttrium YCa
4O (BO
3)
3
Lime borate oxygen gadolinium GdCa
4O (BO
3)
3
Neodymium-doped Nd
3+Lime borate oxygen yttrium Nd
xY
1-xCa
4O (BO
3)
3Or
Neodymium-doped Nd
3+Lime borate oxygen gadolinium Nd
xGd
1-xCa
4O (BO
3)
3Wherein, Nd
3+Doping content x is 0.001-0.25at.;
2). step 1) is taken by weighing raw material mix, and put people's platinum crucible behind the mould briquetting of packing into, carry out sintering, sintering temperature 1000-1400 ℃, obtain described lime borate oxonium salt polycrystal;
3) step 2) polycrystal of the lime borate oxonium salt that obtains puts into Iridium Crucible, and charged Iridium Crucible is put into single crystal growing furnace vacuumize, and shielding gas nitrogen is gone in inflation; Adopt the mode of heating in medium frequency, be warmed up to the polycrystal fusing, cooling is afterwards condensed it, the polycrystal that is warming up to the lime borate oxonium salt once more melts, and repeatedly at least twice, bubble is Removed All, after hot 20-50 ℃, constant temperature 0.5-3 hour, the lime borate oxonium salt polycrystal liquation that obtains melting;
4), find out the direction of this lime borate oxonium salt crystal nonlinear factor maximum by X-ray diffraction technology, and be complementary crystal that direction cuts out as seed crystal along optimum bit with a lime borate oxonium salt crystal with conventional direction growth;
5) with step 4) with optimum bit be complementary that direction cuts seed crystal put into single crystal growing furnace, and slowly deliver to vertically downward in the polycrystal liquation that step 3) obtains, the top of seed crystal is contacted with lime borate oxonium salt polycrystal liquation gets final product; And keep seed crystal to grow perpendicular to the direction of lime borate oxonium salt polycrystal liquid level, be to be the direction growth that is complementary along optimum bit; Afterwards by receiving neck, shouldering, three technological processs of ending;
Wherein, when receiving the neck growth, pull rate is 2-10mm/ hour, and when the seed crystal radius was received to 1～1.5mm, beginning was with 0.5-20 degree/hour slowly cooling; Carry out shouldering again, pull rate was reduced to 0.5～2mm/ hour; When the diameter of crystal shoulder reaches 20-40mm, again with the 0.5-10 degree/hour speed heat up, carry out isodiametric growth; Prepare to carry to take off crystal when crystal lifts to the 20-50 millimeter, its concrete operations of putting forward the process of taking off are as follows:
With 20-50 degree/hour slow elevated temperature, treat temperature rising 1-10 degree, the crystal bottom of lime borate oxonium salt is the time receiving inwardly, pulling rate was increased to 5-20mm/ hour, crystal and liquation are broken away from, be 20-50 degree/hour reduce to room temperature then with the rate of temperature fall, obtain along the be complementary lime borate oxonium salt crystal of direction growth of optimum bit.
2. by the described lime borate oxonium salt crystalline growth method of claim 1, it is characterized in that comprise also that crystal after coming out of the stove is placed in the resistance furnace to anneal that annealing temperature is 900 ℃-1200 ℃, annealing time is 5-12 hour with frequency-doubled effect.
3. by the described lime borate oxonium salt crystalline growth method of claim 1, it is characterized in that carrying out crystal pulling method when growing, need be added with a spot of oxygen in protective atmosphere, its oxygen content is the 1-5% of volume ratio with frequency-doubled effect.
4. by the described lime borate oxonium salt crystalline growth method of claim 1, it is characterized in that described seed crystal is shaped as rectangular parallelepiped, right cylinder or arbitrary shape with frequency-doubled effect.
5. by the described lime borate oxonium salt crystalline growth method of claim 1, it is characterized in that with frequency-doubled effect, in the receipts neck growth of step 5), 10～30 rev/mins of the rotating speeds of crystal growth.
6. by the described lime borate oxonium salt crystalline growth method of claim 1, it is characterized in that the cut direction of described seed crystal is with frequency-doubled effect:
For Nd:YCOB or YCOB crystal, the direction of growth is: θ=113 ° ± 5 °, φ=36.5 ° ± 5 °; Or θ=67 ° ± 5 °, φ=143 ° ± 5 °;
For Nd:GdCOB or GdCOB crystal, the direction of growth is: θ=113 ° ± 5 °, φ=47.5 ° ± 5 °; Or θ=67 ° ± 5 °, φ=132.5 ° ± 5 °.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 201010272983 CN101942699A (en) | 2010-09-03 | 2010-09-03 | Method for growing calcium borate oxysalt crystal with frequency multiplication effect |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 201010272983 CN101942699A (en) | 2010-09-03 | 2010-09-03 | Method for growing calcium borate oxysalt crystal with frequency multiplication effect |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN101942699A true CN101942699A (en) | 2011-01-12 |
Family
ID=43434891
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 201010272983 Pending CN101942699A (en) | 2010-09-03 | 2010-09-03 | Method for growing calcium borate oxysalt crystal with frequency multiplication effect |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN101942699A (en) |
Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102061513A (en) * | 2011-01-27 | 2011-05-18 | 中国科学院上海硅酸盐研究所 | Method for preparing large size calcium-rare earth borate crystal |
| CN102660774A (en) * | 2012-04-25 | 2012-09-12 | 中国科学院福建物质结构研究所 | Boric acid oxygen cadmium ytterbium as nonlinear optical crystal |
| CN103628138A (en) * | 2013-12-05 | 2014-03-12 | 山东大学 | Large-size mass terbium calcium oxide borate crystal, and growth and application of crystal |
| CN104451881A (en) * | 2014-12-19 | 2015-03-25 | 单县晶瑞光电有限公司 | Neodymium-doped yttrium calcium oxytriborate crystal growing method |
| CN104862774A (en) * | 2015-05-20 | 2015-08-26 | 山东大学 | High-temperature YxGd(1-x)Ca4O(BO3)3 piezoelectric crystal material as well as growth method and application thereof |
| CN105071217A (en) * | 2015-08-27 | 2015-11-18 | 山东大学 | Self-frequency-doubling all-solid-state yellow-light laser |
| CN105112990A (en) * | 2015-10-12 | 2015-12-02 | 山东大学 | Micro-pulling-down orientated growth method of special-shaped frequency doubling crystal similar to device size |
| CN106801257A (en) * | 2016-03-24 | 2017-06-06 | 山东大学 | One kind mixes ytterbium crystal and its growing method and application |
| CN109659806A (en) * | 2019-02-22 | 2019-04-19 | 山东大学 | A kind of temperature-insensitive type frequency-doubling crystal device and its application |
| CN110273180A (en) * | 2018-03-14 | 2019-09-24 | 中国科学院理化技术研究所 | Near match angle Al adulterates CsLiB6O10The growing method and optical application of crystal |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1146812A (en) * | 1995-02-21 | 1997-04-02 | 克里斯马特克公司 | Non-linear crystals and use thereof |
| CN1237655A (en) * | 1999-06-11 | 1999-12-08 | 山东大学 | Specially angle-cut boric acid oxygen calcium rare earth salt laser frequency doubling crystal |
-
2010
- 2010-09-03 CN CN 201010272983 patent/CN101942699A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1146812A (en) * | 1995-02-21 | 1997-04-02 | 克里斯马特克公司 | Non-linear crystals and use thereof |
| CN1237655A (en) * | 1999-06-11 | 1999-12-08 | 山东大学 | Specially angle-cut boric acid oxygen calcium rare earth salt laser frequency doubling crystal |
Non-Patent Citations (5)
| Title |
|---|
| > 20000531 张树君等 GaCa4O(BO3)3:Yb晶体沿倍频方向的生长和自倍频性质 126-129 1-6 第29卷, 第2期 2 * |
| > 20001231 Huaijin Zhang et al. Growth and self-frequency doubling laser output of Nd:Ca4Gd0.275Y0.725O(BO3)3 crystal 815-818 1-6 第210卷, 2 * |
| > 20001231 Shujun Zhang et al. Growth of NdxGd1-xCa4O(BO3)3 along phase matching direction and passive mode-locking self-frequency-doubling characteristics 217-221 1-6 第212卷, 2 * |
| > 20011231 江怀东等 GdCOB晶体的生长及二倍频性质 124-126 1-6 第12卷, 第12期 2 * |
| > 20020930 王正平等 Nd:Ca4ReO(BO3)3(Re=Gd,Y)晶体最佳激光、最佳倍频及最佳自倍频方向的确定 1-6 第51卷, 第9期 2 * |
Cited By (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102061513A (en) * | 2011-01-27 | 2011-05-18 | 中国科学院上海硅酸盐研究所 | Method for preparing large size calcium-rare earth borate crystal |
| CN102660774A (en) * | 2012-04-25 | 2012-09-12 | 中国科学院福建物质结构研究所 | Boric acid oxygen cadmium ytterbium as nonlinear optical crystal |
| CN103628138A (en) * | 2013-12-05 | 2014-03-12 | 山东大学 | Large-size mass terbium calcium oxide borate crystal, and growth and application of crystal |
| CN104451881A (en) * | 2014-12-19 | 2015-03-25 | 单县晶瑞光电有限公司 | Neodymium-doped yttrium calcium oxytriborate crystal growing method |
| CN104862774B (en) * | 2015-05-20 | 2018-01-02 | 山东大学 | A kind of line borate oxygen yttrium gadolinium high-temperature piezoelectric crystalline material and its growing method and application |
| CN104862774A (en) * | 2015-05-20 | 2015-08-26 | 山东大学 | High-temperature YxGd(1-x)Ca4O(BO3)3 piezoelectric crystal material as well as growth method and application thereof |
| CN105071217A (en) * | 2015-08-27 | 2015-11-18 | 山东大学 | Self-frequency-doubling all-solid-state yellow-light laser |
| CN105071217B (en) * | 2015-08-27 | 2017-10-24 | 山东大学 | It is a kind of from frequency multiplication all-solid-state yellow laser |
| CN105112990A (en) * | 2015-10-12 | 2015-12-02 | 山东大学 | Micro-pulling-down orientated growth method of special-shaped frequency doubling crystal similar to device size |
| CN105112990B (en) * | 2015-10-12 | 2018-07-06 | 山东大学 | A kind of method of the special-shaped nearly device frequency-doubling crystal of micro- drop-down oriented growth |
| CN106801257A (en) * | 2016-03-24 | 2017-06-06 | 山东大学 | One kind mixes ytterbium crystal and its growing method and application |
| CN110273180A (en) * | 2018-03-14 | 2019-09-24 | 中国科学院理化技术研究所 | Near match angle Al adulterates CsLiB6O10The growing method and optical application of crystal |
| CN109659806A (en) * | 2019-02-22 | 2019-04-19 | 山东大学 | A kind of temperature-insensitive type frequency-doubling crystal device and its application |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN101942699A (en) | Method for growing calcium borate oxysalt crystal with frequency multiplication effect | |
| CN100507093C (en) | Fluxing medium growing method for fluoroboric acid calcium non-linear optical crystal | |
| CN100425743C (en) | Process for growing gallium nitride single crystal utilizing new flux molten-salt growth method | |
| CN101476156A (en) | Gadolinium, yttrium, scandium and gallium doped garnet, gadolinium-yttrium-scandium-gallium-aluminum garnet and crystal growth method by melt method | |
| CN101597790A (en) | The method of preparing cast polycrystalline silicon through melting silicon and doping nitrogen under nitrogen | |
| CN101225545A (en) | Method for preparing near-stoichiometric lithium tantalate crystals | |
| CN101597787B (en) | Method for casting nitrogen-doped monocrystalline silicon with controllable nitrogen concentration under nitrogen | |
| CN101591807A (en) | Directionally solidified casting monocrystalline silicon of nitrating and preparation method thereof | |
| CN101701355A (en) | Pulling growth method of neodymium-doped yttrium-calcium aluminate laser crystal | |
| CN101603206B (en) | Method for preparing Cr<3+>, Nd<3+>:YVO4 crystal and Cr<4+>, Nd<3+>:YVO4 crystal | |
| CN101514491A (en) | Ba3BP3O12 crystalloid, growing method and application thereof | |
| CN103422172A (en) | High-performance photoelectric functional calcium borate thulium oxide crystal and growth and application thereof | |
| CN102828247A (en) | Preparation method of erbium-doped calcium yttrium aluminate laser crystal | |
| CN110067024A (en) | Photoelectric functional crystal M3RE(PO4)3And preparation method thereof | |
| CN102443853A (en) | Preparation method of rare earth ion-doped large lead tungstate crystal | |
| CN109652856A (en) | Tb3+Self-activated laser crystal, preparation method and the application in visible waveband solid state laser | |
| CN105133004A (en) | USb2 monocrystal fluxing agent growth method and product prepared in same | |
| CN101871126A (en) | Gadolinium gallate crystal and growth method thereof | |
| CN100572615C (en) | A kind of alkali metal borate compounds and monocrystalline thereof and preparation method | |
| CN102383186B (en) | Pulling method for growing Ca12Al14O33 monocrystal in non-stoichiometric ratio melt | |
| CN112647131B (en) | Gadolinium lithium zirconate compound and preparation method and application of single crystal thereof | |
| CN1122732C (en) | Non-linear optical crystal of magnesium zinc bromophosphate and its preparing process and application | |
| CN109868502B (en) | Rare earth doped niobate monocrystal up-conversion luminescent material and preparation method thereof | |
| CN104141170A (en) | Method for growth of compound cadmium sodium borate crystal | |
| CN1322174C (en) | Technique for developing crystal of bismuth boric acid through falling curcible method |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C02 | Deemed withdrawal of patent application after publication (patent law 2001) | ||
| WD01 | Invention patent application deemed withdrawn after publication |
Open date: 20110112 |