CN1379125A - Non-linear optical crystal of magnesium zinc bromophosphate and its preparing process and application - Google Patents
Non-linear optical crystal of magnesium zinc bromophosphate and its preparing process and application Download PDFInfo
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- CN1379125A CN1379125A CN 01109760 CN01109760A CN1379125A CN 1379125 A CN1379125 A CN 1379125A CN 01109760 CN01109760 CN 01109760 CN 01109760 A CN01109760 A CN 01109760A CN 1379125 A CN1379125 A CN 1379125A
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Abstract
A non-linear optical crystal of magnesium zine bromophosphate can be used to make a non-linear optical device and has the chemical formula: MgxZn3-xBPO7, where x is greater than 0 and less than 3. It is prepared through proportioning the chemicals containing Mg, Zn, B and P in mole ratio of x:3-x:1:1, grinding, mixing, pre-calcining, sintering, smelting in crucible, keeping the temp. higher than smelting point for 1-20 hr, cooling to temp. 1-5 deg.c higher than smelting point, and quickly growing crystal.
Description
The present invention relates to a kind of non-linear optic crystal and its production and use, particularly a kind of non-linear optical crystal of magnesium zinc bromophosphate and its production and use.
In modern laser, the frequency inverted crystal receives much concern owing to effectively widening the Wavelength of Laser scope.Utilize crystalline frequency-doubled effect, mixing effect and tunable optical parametric oscillation effect, can make second harmonic generator, upper and lower frequency converter, device for non-linear optical such as optical parametric oscillator.The laser that laser apparatus produces can carry out frequency inverted by device for non-linear optical, thereby obtains the laser of how useful wavelength, and this is the important means that obtains new LASER Light Source.The full blue green light laser system of solidifying can produce near-infrared laser by solid statelaser and carries out frequency inverted through non-linear optic crystal again and realize, has great application prospect at laser technology field.
Frequency-doubled effect is most important non-linear optical effect.A branch of frequency is that to produce a branch of frequency after by a non-linear optic crystal be that the frequency multiplication light wave of 2 ω is called frequency-doubled effect for the fundamental light wave of ω.Crystal as laser freuqency doubling must be realized phase matched, and when satisfying phase-matching condition, the crystalline frequency-doubling conversion efficiency just can reach maximum value.Common available angle phase matched method realizes phase matched, selects a certain specific direction of crystalline that is:, and fundamental frequency light equates with the specific refractory power of frequency doubled light on this direction, and laser is propagated along this direction just can satisfy phase-matching condition.For uniaxial crystal, phase matched is relevant with the θ angle, and the θ angle is the angle between crystalline optical axis and the incident light direction; For biaxial crystal, phase matched is determined jointly that by θ, angle the angle is incident light direction position angle.
The main nonlinear optical material that is applied to the frequency conversion of blue green light wave band at present has KTP (KTiOPO
4) crystal (referring to USA Magazine " Journal of Applied Physics ", Vol.47,4980,1976), " Chinese science " B, Vol. (28), the BBO (β-BaB that introduces in 235,1985
2O
4) crystal and disclosed LBO (LiB in No. 88102084, " Chinese invention patent "
3O
5) crystal.These materials have weak point in crystal growth: because KTP and LBO right and wrong are with the composition melting compound, and BBO has phase transformation under fusing point, they all must use flux method to grow, the speed of growth is slow, be difficult for obtaining large-size crystals, the cost height has influenced the large-scale application of full curing blue-green Laser.Thereby in recent years, when the development novel nonlinear optical crystal, not only pay attention to crystalline optical property and mechanical property, and more and more pay attention to crystalline and prepare characteristic, wish that new crystalline material prepares easily, preferably the melt method for growing monocrystalline can be used, thereby the non-linear optic crystal of cheap large-size high-quality can be obtained.The melt method for growing technology has multiple, crystal pulling method for example, and crucible moves method, top-seeded solution growth or the like, its know-why has many treatises.
The Z.Kristallogr. magazine (Vol.160,135-137,1982) of Germany has been reported low temperature phase boron zinc phosphate α-Zn
3BPO
7With low temperature boron trimagnesium phosphate α-Mg mutually
3BPO
7Existence, α-Zn
3BPO
7Belong to rhombic system, spacer is Imm2, and unit cell parameters is a=8.438 (5) , b=4.884 (5) , c=12.746 (5) ; α-Mg
3BPO
7Also belong to rhombic system, spacer is Imm2, and unit cell parameters is a=8.497 (5) , b=4.880 (5) , c=12.558 (5) .All there is phase transformation in these two kinds of compounds, and their crystal growth is all had any problem.
The object of the present invention is to provide a kind of chemical formula is Mg
xZn
3-xBPO
7, the non-linear optical crystal of magnesium zinc bromophosphate of 0＜x＜3 and a kind of fusing assistant that need not to use, the method for preparing non-linear optical crystal of magnesium zinc bromophosphate simple to operate and the purposes of non-linear optical crystal of magnesium zinc bromophosphate are provided.
Embodiment of the present invention is as follows:
Non-linear optical crystal of magnesium zinc bromophosphate provided by the invention is characterized in that, this crystal is by chemical formula Mg
xZn
3-xBPO
7Statement, wherein 0＜x＜3; Do not have symmetry centre, be biaxial crystal, belong to rhombic system, spacer is Imm2, and is transparent in 200～2500nm wavelength region, and Mohs' hardness is 5.0.
The preparation method of non-linear optical crystal of magnesium zinc bromophosphate provided by the invention, its processing step is as follows:
A. prepare melt: the compound that will contain Mg, Zn, B and P is x: 3-x in molar ratio: 1: 1 proportioning is prepared burden, and ground and mixed is even, behind pre-burning and sintering, in crucible, be heated to fusing, be cooled to the temperature that is higher than 1～5 ℃ of fusing point again, make melt, stand-by;
B. use melting method quick growing crystal in melt: described melting method comprises that top-seeded solution growth, crystal pulling method and crucible move method;
The step of described top-seeded solution growth growing crystal is: seed crystal is fixed on the seed rod, seed crystal contacts with the bath surface that above-mentioned steps a prepares in crucible under the top, with rotating speed rotation seed crystal and/or the crucible of 0.1～80rpm, with 0.1～5 ℃/day speed cooling growth; After growth is finished, make crystal break away from melt liquid level, the speed annealing with 10～100 ℃/hour stops heating then, and furnace cooling promptly makes non-linear optical crystal of magnesium zinc bromophosphate of the present invention;
The step of described Czochralski grown crystal is: seed crystal is fixed on the seed rod, seed crystal contacts with the bath surface that above-mentioned steps a prepares in earthenware under the top, with the rotating speed of 0.1～80rpm rotation seed crystal and/or crucible, with 0.01～5mm/ hour the speed pulling crystal that makes progress; After growth finishes, make crystal break away from melt liquid level, the speed annealing with 10～100 ℃/hour stops heating then, and furnace cooling promptly makes non-linear optical crystal of magnesium zinc bromophosphate to room temperature;
The step that described crucible moves the method growing crystal is: with 0.01～8mm/ hour speed mobile crucible or well heater or slowly crystal growing furnace is lowered the temperature, melt is solidified by a temperature gradient zone generate non-linear optical crystal of magnesium zinc bromophosphate, described well heater is resistance heater, elema heater or Si-Mo rod well heater; Described crucible be the bottom with the cylinder shape of conical wedge angle or the crucible of boat type, described moving to moving horizontally or vertical shifting;
In principle, existing melt growth technology can be used for preparing magnesium zinc bromophosphate crystal non-linear optic crystal of the present invention, can obtain the magnesium zinc bromophosphate crystal non-linear optic crystal of corresponding large-size when adopting the large size crucible.
Wherein, the raw materials of compound of the described Mg of containing comprises magniferous corresponding oxide, oxyhydroxide, muriate, carbonate, nitrate, vitriol, acetate or oxalate; The raw materials of compound of the described Zn of containing comprises zinciferous corresponding oxide compound, oxyhydroxide, muriate, carbonate, nitrate, vitriol, acetate or oxalate; The raw materials of compound of the described B of containing comprises H
3BO
3Or B
2O
3The raw materials of compound of the described P of containing comprises P
2O
5, NH
4H
2PO
4Or (NH
4)
2HPO
4The crystal optics working method is as follows: according to crystalline crystallography data, with crystal blank orientation, by required phase matching angle θ and , thickness and sectional dimension sliced crystal, with the logical light mirror polish of crystal, promptly can be used as device for non-linear optical and use.The x value of magnesium zinc bromophosphate crystal non-linear optic crystal is depended in the selection of phase matching angle θ and .About the details of biaxial crystal phase matching angle θ and referring to USA Magazine " Journalof Applied Physics ", Vol.38,4365,1973.The optics working method of above-mentioned non-linear optic crystal is the content that those skilled in the art are familiar with.Crystal provided by the present invention does not have particular requirement to the optics working accuracy.
The purposes of magnesium zinc bromophosphate crystal non-linear optic crystal provided by the invention is to be used to make device for non-linear optical, and this device is to comprise a branch of at least incidence electromagnetic radiation is produced the device that a branch of at least frequency is different from the output radiation of incidence electromagnetic radiation after by at least one this non-linear optical crystal of magnesium zinc bromophosphate.
Chemical formula provided by the invention is Mg
xZn
3-xBPO
7The preparation method of the non-linear optical crystal of magnesium zinc bromophosphate of 0＜x＜3 and the existing non-linear optic crystal KTP that is applied to the frequency conversion of blue green light wave band, BBO, the LBO technology of preparing is compared, because this magnesium zinc bromophosphate is fit to use the melt method for growing monocrystalline, general melt growth method can be used, and the melt viscosity of magnesium zinc bromophosphate of the present invention is lower than general borate, be beneficial to mass transport, crystal is grown up and transparent nothing parcel easily, and having does not need to use fusing assistant, simple to operate, fast growth, cost is low, obtains advantages such as large-size crystal easily; The crystal growth cycles such as BBO, LBO, KTP reach 1 month down to the several months, and the magnesium zinc bromophosphate crystal growth cycle of the present invention only needs several days; Compare with non-linear optic crystals such as the BBO, the LBO that use always in the prior art, KTP, this non-linear optical crystal of magnesium zinc bromophosphate has better crystal and prepares characteristic, can use the melt method for growing monocrystalline, obtain cheap large-size high-quality non-linear optic crystal, and this crystal has good mechanical property, not easily broken, deliquescence is not easy to advantages such as processing and preservation.
Further describe the present invention below in conjunction with drawings and Examples:
Accompanying drawing 1 is the non-linear optical crystal of magnesium zinc bromophosphate picture that the present invention prepares;
Accompanying drawing 2 is that the non-linear optical crystal of magnesium zinc bromophosphate that the present invention prepares sees through spectrum;
Accompanying drawing 3 is the fundamental diagrams that typically adopt the device for non-linear optical that non-linear optical crystal of magnesium zinc bromophosphate that the present invention prepares makes.
Wherein: laser apparatus 1 incoming beam 2 non-linear optical crystal of magnesium zinc bromophosphate 3
Accompanying drawing 1 is the picture of the non-linear optical crystal of magnesium zinc bromophosphate of the present invention's preparation; Accompanying drawing 2 is the spectrum that sees through of this non-linear optical crystal of magnesium zinc bromophosphate; As shown in Figure 1, the non-linear optical crystal of magnesium zinc bromophosphate of method preparation of the present invention is by chemical formula Mg
xZn
3-xBPO
7, 0＜x＜3 statements; This crystal is transparent, and ultraviolet absorption edge is the 200nm (see figure 2), and Mohs' hardness is 5.0, is easy to cutting, polishing processing and preservation, and deliquescence is not suitable for making device for non-linear optical.
The drawing of Fig. 3 is described as follows: send light beam 2 by laser apparatus 1 and inject non-linear optical crystal of magnesium zinc bromophosphate 3, the outgoing beam 4 that is produced passes through filter plate 5, thereby obtains needed laser beam.This device for non-linear optical can be the frequency multiplication producer, upper and lower frequency converter, optical parametric oscillator etc.Laser apparatus 1 can be neodymium-doped yttrium-aluminum garnet (Nd:YAG) laser apparatus or other laser apparatus, do the frequency doubling device of light source using the Nd:YAG laser apparatus, incoming beam 2 is that wavelength is the infrared light of 1064nm, producing wavelength by non-linear optical crystal of magnesium zinc bromophosphate is the green frequency doubled light of 532nm, it is the infrared light of 1064nm and the green glow of 532nm that outgoing beam 4 contains wavelength, the effect of filter plate 5 is elimination infrared light compositions, only allows green frequency doubled light to pass through.
In melt, adopt Czochralski grown non-linear optical crystal of magnesium zinc bromophosphate of the present invention:
With 51.515 gram Mg (OH)
2, 391.86 gram Zn (NO
3)
26H
2O, 45.248 gram H
3BO
3With 96.641 gram (NH
4)
2HPO
4Mix back (its mol ratio is Mg: Zn: B: P=1.2.: 1.8: 1: 1), 450 ℃ of pre-burnings 10 hours, then 1000 ℃ of sintering 24 hours, the sample that is obtained is packed in the opening platinum crucible of Φ 60mm * 40mm, crucible is put into crystal growing furnace, fusing heats up, behind the constant temperature 10 hours, be cooled to and be higher than 5 ℃ of Tcs, then seed crystal is fixed on the lower end of seed rod, import crucible from furnace roof portion aperture, make seed crystal contact the beginning crystal growth with melt liquid level.Seed rod speed of rotation 20rpm, pull rate is 0.5mm/ hour; Finish growth and make crystal break away from melt liquid level, be cooled to 100 ℃, stop heating then, make the crystal furnace cooling, obtain to be of a size of the non-linear optical crystal of magnesium zinc bromophosphate of 20mm * 15mm * 7mm to room temperature with 80 ℃/hour speed annealing.
In melt, adopt Czochralski grown non-linear optical crystal of magnesium zinc bromophosphate crystal of the present invention:
With 14.882 gram MgCl
26H
2O, 342.705 gram ZnSO
4, 25.481 the gram B
2O
3With 51.95 gram P
2O
5Mix back (its mol ratio is Mg: Zn: B: P=0.1.: 2.9: 1: 1), 400 ℃ of pre-burnings 10 hours, then 850 ℃ of sintering 24 hours, the sample that is obtained is packed in the opening platinum crucible of Φ 60mm * 40mm, crucible is put into crystal growing furnace, fusing heats up, behind the constant temperature 5 hours, be cooled to and be higher than 4 ℃ of Tcs, then seed crystal is fixed on the lower end of seed rod, import crucible from furnace roof portion aperture, make seed crystal contact the beginning crystal growth with melt liquid level.Seed rod speed of rotation 40rpm, pull rate is 0.4mm/ hour; When finishing growth, make crystal break away from melt liquid level, be cooled to 100 ℃, stop heating then, make the crystal furnace cooling, promptly obtain non-linear optical crystal of magnesium zinc bromophosphate to room temperature with 40 ℃/hour speed annealing.
Adopt top-seeded solution growth to prepare non-linear optical crystal of magnesium zinc bromophosphate:
With 52.170 gram MgSO
4, 217.401 the gram ZnCO
3, 25.147 the gram B
2O
3With 83.09 gram NH
4H
2PO
4Mix (its mol ratio is Mg: Zn: B: P=0.6: 2.4: 1: 1), 450 ℃ of pre-burnings 10 hours, then 900 ℃ of sintering 24 hours, the sample that is obtained is put into the opening platinum crucible of Φ 50mm * 40mm, crucible is put into crystal growing furnace, fusing heats up, behind the constant temperature 20 hours, be cooled to and be higher than 2 ℃ of Tcs, seed crystal is fixed on the seed rod lower end with platinum filament, from furnace roof portion aperture seed crystal is imported crucible, seed crystal is contacted with melt liquid level, and seed rod speed of rotation 25rpm is with 0.5 ℃/day speed cooling, after crystal growth finishes, crystal is lifted from melt liquid level, be cooled to 100 ℃, stop heating with 100 ℃/hour speed annealing, furnace cooling obtains the non-linear optical crystal of magnesium zinc bromophosphate of 14mm * 10mm * 3.5mm to room temperature.
Adopt top-seeded solution growth to prepare non-linear optical crystal of magnesium zinc bromophosphate:
With 56.42 gram MgO, 69.573 gram Zn (OH)
2, 43.281 the gram H
3BO
3With 80.514 gram NH
4H
2PO
4Mix (its mol ratio is Mg: Zn: B: P=2: 1: 1: 1), 450 ℃ of pre-burnings 20 hours, then 1100 ℃ of sintering 30 hours, the sample that is obtained is put into the opening platinum crucible of Φ 60mm * 40mm, crucible is put into crystal growing furnace, fusing heats up, behind the constant temperature 2 hours, be cooled to and be higher than 1 ℃ of Tc, seed crystal is fixed on the seed rod lower end with platinum filament, from furnace roof portion aperture seed crystal is imported crucible, seed crystal is contacted with melt liquid level, and seed rod speed of rotation 15rpm is with 0.5 ℃/day speed cooling, after crystal growth finishes, crystal is lifted from melt liquid level, be cooled to 100 ℃, stop heating with 100 ℃/hour speed annealing, furnace cooling promptly obtains non-linear optical crystal of magnesium zinc bromophosphate to room temperature.
Adopt crucible to move legal system and be equipped with non-linear optical crystal of magnesium zinc bromophosphate:
With 1.363 gram MgO, 3.361 gram Zn (OH)
2, 0.785 the gram B
2O
3With 1.6 gram P
2O
5Mix (its mol ratio is Mg: Zn: B: P=1.5: 1.5: 1: 1), pack in the platinum crucible of Φ 10mm, the conical wedge angle of crucible bottom band, seed crystal is placed crucible bottom, crucible is put into the vertical process furnace, be warming up to after raw material melts fully, keep heating power constant, speed decline crucible with 0.5mm/ hour makes melt solidify the generation monocrystalline from bottom to top.Crystallization finishes and lowers the temperature 100 ℃ with 50 ℃/hour speed annealing, stops heating, and furnace cooling obtains to be of a size of the non-linear optical crystal of magnesium zinc bromophosphate of Φ 10mm * 30mm to room temperature.
Embodiment 6
Adopt crucible to move legal system and be equipped with non-linear optical crystal of magnesium zinc bromophosphate:
With 2.317 gram MgO, 0.936 gram ZnO, 0.801 gram B
2O
3With 1.632 gram P
2O
5Mix (its mol ratio is Mg: Zn: B: P=2.5: 0.5: 1: 1), pack in the platinum crucible of Φ 12mm, the conical wedge angle of crucible bottom band, seed crystal is placed crucible bottom, crucible is put into the vertical process furnace, be warming up to after raw material melts fully, keep heating power constant, speed decline crucible with 0.1mm/ hour makes melt solidify the generation monocrystalline from bottom to top.Crystallization finishes and lowers the temperature 100 ℃ with 30 ℃/hour speed annealing, stops heating, and furnace cooling obtains the sosoloid of magnesium zinc bromophosphate non-linear optic crystal to room temperature.
Embodiment 7
Measure the transmitted spectrum of sosoloid of magnesium zinc bromophosphate non-linear optic crystal in 200～2500nm scope of embodiment 1 gained, this crystal is transparent in whole measurement range; Its Mohs' hardness is 5.0, and is not easily broken, is easy to cutting, polishing processing and preservation, not deliquescence; Described crystal is made sectional dimension 4.5 * 4.5mm, the frequency doubling device of optical direction thickness 5mm, be located at 3 position by accompanying drawing 3 shown devices, at room temperature, make light source with transferring Q Nd:YAG laser apparatus, incident wavelength is 1064nm, by transferring Q Nd:YAG laser apparatus 1 to send wavelength is that the infrared beam 2 of 1064nm is injected this non-linear optical crystal of magnesium zinc bromophosphate 3, producing wavelength is the green frequency doubled light of 532nm, it is the infrared light of 1064nm and the green glow of 532nm that outgoing beam 4 contains wavelength, filter plate 5 elimination infrared light compositions obtain the green laser that wavelength is 532nm.
Those of ordinary skill in the art uses similar method to be not difficult to use Mg
xZn
3-xBPO
7, 0＜x＜3 non-linear optic crystals produce other device for non-linear optical, and as above, the device in the lower frequency transmodulator etc., these all do not exceed design of the present invention and scope.
Claims (10)
1. a non-linear optical crystal of magnesium zinc bromophosphate is characterized in that, this non-linear optical crystal of magnesium zinc bromophosphate is by chemical formula Mg
xZn
3-xBPO
7Statement, wherein 0＜x＜3 do not have symmetry centre, belong to rhombic system, and spacer is Imm2, and is transparent in 200～2500nm wavelength region, and Mohs' hardness is 5.0.
2. the preparation method of the described non-linear optical crystal of magnesium zinc bromophosphate of claim 1 is characterized in that, processing step is as follows:
A. prepare melt: the compound that will contain Mg, Zn, B and P is x: 3-x in molar ratio: 1: 1 batching, behind former abrasive lapping mixing, behind pre-burning and sintering, in crucible, be heated to fusing, be cooled to the temperature that is higher than 1～5 ℃ of fusing point again, make melt, stand-by;
B. use the melt method for growing crystal in melt, described melting method comprises that top-seeded solution growth, crystal pulling method and crucible move method.
3. by the described non-linear optical crystal of magnesium zinc bromophosphate preparation method of claim 2, it is characterized in that the raw materials of compound of the described Mg of containing comprises magniferous corresponding oxide, oxyhydroxide, muriate, carbonate, nitrate, vitriol, acetate or oxalate.
4. press the preparation method of the described preparation non-linear optical crystal of magnesium zinc bromophosphate of claim 2, it is characterized in that the raw materials of compound of the described Zn of containing comprises zinciferous corresponding oxide compound, oxyhydroxide, muriate, carbonate, nitrate, vitriol, acetate or oxalate.
5. by the preparation method of the described preparation non-linear optical crystal of magnesium zinc bromophosphate of claim 2, it is characterized in that the raw materials of compound of the described B of containing comprises H
3BO
3, B
2O
3
6. by the preparation method of the described preparation non-linear optical crystal of magnesium zinc bromophosphate of claim 2, it is characterized in that the raw materials of compound of the described P of containing comprises P
2O
5, NH
4H
2PO
4Or (NH
4)
2HPO
4
7. by the described non-linear optical crystal of magnesium zinc bromophosphate preparation method of claim 2, it is characterized in that, the step of described top-seeded solution growth is: seed crystal is fixed on the seed rod, seed crystal contacts with the bath surface that above-mentioned steps a prepares in crucible under the top, with rotating speed rotation seed crystal and/or the crucible of 0.1～80rpm, with 0.1～5 ℃/day speed cooling growth; After growth is finished, make crystal break away from melt liquid level, the speed annealing with 10～100 ℃/hour stops heating then, and furnace cooling promptly makes non-linear optical crystal of magnesium zinc bromophosphate of the present invention.
8. by the described non-linear optical crystal of magnesium zinc bromophosphate preparation method of claim 2, it is characterized in that, the step of described crystal pulling method is: seed crystal is fixed on the seed rod, seed crystal contacts with the bath surface that above-mentioned steps a prepares in crucible under the top, with the rotating speed of 0.1～80rpm rotation seed crystal and/or crucible, with 0.01～5mm/ hour the speed pulling crystal that makes progress; After growth finishes, make crystal break away from melt liquid level, the speed annealing with 10～100 ℃/hour stops heating then, and furnace cooling promptly makes boron trimagnesium phosphate non-linear optic crystal to room temperature.
9. by the described non-linear optical crystal of magnesium zinc bromophosphate preparation method of claim 2, it is characterized in that, the step of described falling crucible method is: with 0.01～8mm/ hour speed mobile crucible or well heater or slowly crystal growing furnace is lowered the temperature, melt is solidified by a temperature gradient zone generate non-linear optical crystal of magnesium zinc bromophosphate, described well heater is resistance heater, elema heater or Si-Mo rod well heater; Described crucible be the bottom with the cylinder shape of conical wedge angle or the crucible of boat type, described moving to moving horizontally or vertical shifting.
10. the purposes of the described non-linear optical crystal of magnesium zinc bromophosphate of claim 1 is to be used to make device for non-linear optical, and this device for non-linear optical comprises a branch of at least incidence electromagnetic radiation is produced the device that a branch of at least frequency is different from the output radiation of incidence electromagnetic radiation after by at least one this non-linear optical crystal of magnesium zinc bromophosphate.
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|---|---|---|---|
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|---|---|---|---|
| CN 01109760 CN1122732C (en) | 2001-04-10 | 2001-04-10 | Non-linear optical crystal of magnesium zinc bromophosphate and its preparing process and application |
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100361354C (en) * | 2003-09-28 | 2008-01-09 | 中国科学院理化技术研究所 | Application of large-sized boron phosphate non-linear optical crystal |
| CN101216656B (en) * | 2008-01-14 | 2010-06-23 | 武汉大学 | Inorganic infrared nonlinear optical crystal material and method for making same and uses |
| CN101876772B (en) * | 2009-11-19 | 2011-12-28 | 中国科学院新疆理化技术研究所 | Compound potassium lead borophosphate nonlinear optical crystal as well as preparation method and application thereof |
| CN103173859A (en) * | 2011-12-20 | 2013-06-26 | 中国科学院新疆理化技术研究所 | Cadmium sodium borophosphate compound, cadmium sodium borophosphate nonlinear optical crystal, preparation methods of compound and crystal, and use of crystal |
| CN105568381A (en) * | 2014-10-15 | 2016-05-11 | 中国科学院新疆理化技术研究所 | Yttrium phosphate double-refraction crystal and growing method and application thereof |
| CN106835263A (en) * | 2017-02-20 | 2017-06-13 | 中国科学院新疆理化技术研究所 | The preparation method and purposes of lithium fluoroborate nonlinear optical crystal |
-
2001
- 2001-04-10 CN CN 01109760 patent/CN1122732C/en not_active Expired - Fee Related
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100361354C (en) * | 2003-09-28 | 2008-01-09 | 中国科学院理化技术研究所 | Application of large-sized boron phosphate non-linear optical crystal |
| CN101216656B (en) * | 2008-01-14 | 2010-06-23 | 武汉大学 | Inorganic infrared nonlinear optical crystal material and method for making same and uses |
| CN101876772B (en) * | 2009-11-19 | 2011-12-28 | 中国科学院新疆理化技术研究所 | Compound potassium lead borophosphate nonlinear optical crystal as well as preparation method and application thereof |
| CN103173859A (en) * | 2011-12-20 | 2013-06-26 | 中国科学院新疆理化技术研究所 | Cadmium sodium borophosphate compound, cadmium sodium borophosphate nonlinear optical crystal, preparation methods of compound and crystal, and use of crystal |
| CN103173859B (en) * | 2011-12-20 | 2015-05-13 | 中国科学院新疆理化技术研究所 | Cadmium sodium borophosphate compound, cadmium sodium borophosphate nonlinear optical crystal, preparation methods of compound and crystal, and use of crystal |
| CN105568381A (en) * | 2014-10-15 | 2016-05-11 | 中国科学院新疆理化技术研究所 | Yttrium phosphate double-refraction crystal and growing method and application thereof |
| CN106835263A (en) * | 2017-02-20 | 2017-06-13 | 中国科学院新疆理化技术研究所 | The preparation method and purposes of lithium fluoroborate nonlinear optical crystal |
| CN106835263B (en) * | 2017-02-20 | 2020-01-03 | 中国科学院新疆理化技术研究所 | Preparation method and application of lithium fluoroborate nonlinear optical crystal |
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| Publication number | Publication date |
|---|---|
| CN1122732C (en) | 2003-10-01 |
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