CN101775652A - K3Al2(PO4)3Preparation and use of nonlinear optical crystal - Google Patents
K3Al2(PO4)3Preparation and use of nonlinear optical crystal Download PDFInfo
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- CN101775652A CN101775652A CN201010109097A CN201010109097A CN101775652A CN 101775652 A CN101775652 A CN 101775652A CN 201010109097 A CN201010109097 A CN 201010109097A CN 201010109097 A CN201010109097 A CN 201010109097A CN 101775652 A CN101775652 A CN 101775652A
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- 239000013078 crystal Substances 0.000 title claims abstract description 120
- 230000003287 optical effect Effects 0.000 title claims abstract description 23
- 238000002360 preparation method Methods 0.000 claims abstract description 18
- 238000002156 mixing Methods 0.000 claims abstract description 12
- 238000000034 method Methods 0.000 claims abstract description 9
- 238000006243 chemical reaction Methods 0.000 claims abstract description 4
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 36
- 238000001816 cooling Methods 0.000 claims description 18
- 229910052697 platinum Inorganic materials 0.000 claims description 18
- 239000000843 powder Substances 0.000 claims description 15
- 150000001875 compounds Chemical class 0.000 claims description 14
- 239000007788 liquid Substances 0.000 claims description 13
- 238000010792 warming Methods 0.000 claims description 13
- 238000005303 weighing Methods 0.000 claims description 9
- 238000007716 flux method Methods 0.000 claims description 7
- 239000004570 mortar (masonry) Substances 0.000 claims description 7
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 6
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 6
- 238000005245 sintering Methods 0.000 claims description 6
- QNRATNLHPGXHMA-XZHTYLCXSA-N (r)-(6-ethoxyquinolin-4-yl)-[(2s,4s,5r)-5-ethyl-1-azabicyclo[2.2.2]octan-2-yl]methanol;hydrochloride Chemical compound Cl.C([C@H]([C@H](C1)CC)C2)CN1[C@@H]2[C@H](O)C1=CC=NC2=CC=C(OCC)C=C21 QNRATNLHPGXHMA-XZHTYLCXSA-N 0.000 claims description 5
- 125000006850 spacer group Chemical group 0.000 claims description 5
- 229910052782 aluminium Inorganic materials 0.000 claims description 4
- 239000004411 aluminium Substances 0.000 claims description 4
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 4
- PPQREHKVAOVYBT-UHFFFAOYSA-H dialuminum;tricarbonate Chemical compound [Al+3].[Al+3].[O-]C([O-])=O.[O-]C([O-])=O.[O-]C([O-])=O PPQREHKVAOVYBT-UHFFFAOYSA-H 0.000 claims description 4
- 230000005670 electromagnetic radiation Effects 0.000 claims description 4
- 238000000227 grinding Methods 0.000 claims description 4
- 238000012856 packing Methods 0.000 claims description 4
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 claims description 4
- 230000008569 process Effects 0.000 claims description 4
- LWIHDJKSTIGBAC-UHFFFAOYSA-K tripotassium phosphate Chemical compound [K+].[K+].[K+].[O-]P([O-])([O-])=O LWIHDJKSTIGBAC-UHFFFAOYSA-K 0.000 claims description 4
- 238000003746 solid phase reaction Methods 0.000 claims description 3
- BNGXYYYYKUGPPF-UHFFFAOYSA-M (3-methylphenyl)methyl-triphenylphosphanium;chloride Chemical compound [Cl-].CC1=CC=CC(C[P+](C=2C=CC=CC=2)(C=2C=CC=CC=2)C=2C=CC=CC=2)=C1 BNGXYYYYKUGPPF-UHFFFAOYSA-M 0.000 claims description 2
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 claims description 2
- 229910021502 aluminium hydroxide Inorganic materials 0.000 claims description 2
- ILRRQNADMUWWFW-UHFFFAOYSA-K aluminium phosphate Chemical compound O1[Al]2OP1(=O)O2 ILRRQNADMUWWFW-UHFFFAOYSA-K 0.000 claims description 2
- IRXRGVFLQOSHOH-UHFFFAOYSA-L dipotassium;oxalate Chemical compound [K+].[K+].[O-]C(=O)C([O-])=O IRXRGVFLQOSHOH-UHFFFAOYSA-L 0.000 claims description 2
- 230000004927 fusion Effects 0.000 claims description 2
- 230000008676 import Effects 0.000 claims description 2
- 235000006408 oxalic acid Nutrition 0.000 claims description 2
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Substances [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 2
- 235000015320 potassium carbonate Nutrition 0.000 claims description 2
- 239000004323 potassium nitrate Substances 0.000 claims description 2
- 235000010333 potassium nitrate Nutrition 0.000 claims description 2
- CHWRSCGUEQEHOH-UHFFFAOYSA-N potassium oxide Chemical compound [O-2].[K+].[K+] CHWRSCGUEQEHOH-UHFFFAOYSA-N 0.000 claims description 2
- 229910001950 potassium oxide Inorganic materials 0.000 claims description 2
- 229940093916 potassium phosphate Drugs 0.000 claims description 2
- 229910000160 potassium phosphate Inorganic materials 0.000 claims description 2
- 235000011009 potassium phosphates Nutrition 0.000 claims description 2
- 238000002203 pretreatment Methods 0.000 claims description 2
- 230000005855 radiation Effects 0.000 claims description 2
- 238000010671 solid-state reaction Methods 0.000 claims description 2
- 239000000463 material Substances 0.000 abstract description 7
- 230000005540 biological transmission Effects 0.000 abstract description 3
- 239000000203 mixture Substances 0.000 abstract description 3
- 238000010438 heat treatment Methods 0.000 abstract 1
- 238000004519 manufacturing process Methods 0.000 abstract 1
- 238000002844 melting Methods 0.000 abstract 1
- 230000008018 melting Effects 0.000 abstract 1
- 238000003860 storage Methods 0.000 abstract 1
- 239000002994 raw material Substances 0.000 description 6
- 229910019655 synthetic inorganic crystalline material Inorganic materials 0.000 description 5
- 230000000694 effects Effects 0.000 description 4
- 238000004321 preservation Methods 0.000 description 4
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 239000000155 melt Substances 0.000 description 2
- 150000003016 phosphoric acids Chemical class 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- JNDMLEXHDPKVFC-UHFFFAOYSA-N aluminum;oxygen(2-);yttrium(3+) Chemical compound [O-2].[O-2].[O-2].[Al+3].[Y+3] JNDMLEXHDPKVFC-UHFFFAOYSA-N 0.000 description 1
- 230000003321 amplification Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000004455 differential thermal analysis Methods 0.000 description 1
- 230000008030 elimination Effects 0.000 description 1
- 238000003379 elimination reaction Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 238000003199 nucleic acid amplification method Methods 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 238000005498 polishing Methods 0.000 description 1
- 238000004611 spectroscopical analysis Methods 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 229910001428 transition metal ion Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- 229910019901 yttrium aluminum garnet Inorganic materials 0.000 description 1
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Abstract
The invention relates to K3Al2(PO4)3Nonlinear optical crystal, its preparation method and application, the crystal belongs to orthorhombic system, space group is Pna21The unit cell parameters are as follows: a-8.685 (2) , b-16.947 (2) , c-8.458 (3) , α - β - γ -90 °; the preparation method adopts a fluxing agent method to grow the crystal: will K3Al2(PO4)3∶K2O∶P2O5Mixing the materials according to the molar ratio of 1: 0.5-1.5, and placing the mixture in a muffle furnace for heating and melting; then placing the crystal in a single crystal growth furnace, and growing the crystal by adopting a seed crystal method; the K is3Al2(PO4)3The crystal has the advantages of large nonlinear optical effect, wide light transmission range (180-2500nm), good mechanical property, no deliquescence, easy processing and storage, and the like, can be used for manufacturing nonlinear optical devices, and is suitable for blue-green light wave bandAnd the need for ultraviolet band laser frequency conversion.
Description
Technical field
The invention belongs to the preparation field of non-linear optic crystal, particularly chemical formula is K
3Al
2(PO
4)
3The preparation and the purposes of non-linear optic crystal.
Technical background
Crystal with non-linear optical effect is called non-linear optic crystal.Here non-linear optical effect is meant effects such as frequency multiplication and frequency, difference frequency, parameter amplification.Have only crystal just to have non-linear optical effect with symmetry centre.Utilize the crystalline non-linear optical 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 laser apparatus is more widely used.All solid state blue green light laser system can produce near-infrared laser by solid statelaser carries out frequency inverted through non-linear optic crystal again and realizes, has great application prospect at laser technology field.The phosphoric acid salt that is applied to laser frequency at present has KDP (KH
2PO
4), KTP (KTiOPO
4) etc.These crystal are difficult at ultraviolet band and use because uv-absorbing is ended margin system.KDP is because of hydroxyl, and KTP is because contain transition metal ion, has caused the ultraviolet cut-on limit excessive.Therefore in order to expand the application of phosphoric acid salt, be necessary to seek the non-linear optical crystal material that does not contain hydroxyl and transition metal at ultraviolet band.
India Nandini Devi, and R. etc. (Inorganic Chemistry, (2000), 39,2391-2396) reported K
3Al
2(PO
4)
3Crystalline structure, this crystal K
3Al
2(PO
4)
3Belong to rhombic system, not possessing has symmetry centre, and spacer is Pna2
1, unit cell parameters is:
α=β=γ=90 °.Do not see as yet that so far relevant preparation size is enough to the K that uses for physical property measurement
3Al
2(PO
4)
3The crystalline report is not also about K
3Al
2(PO
4)
3Crystal non-linear optical property or with K
3Al
2(PO
4)
3Crystal is used to make the report of device for non-linear optical.
Summary of the invention
The object of the present invention is to provide a kind of K
3Al
2(PO
4)
3Non-linear optic crystal, this K
3Al
2(PO
4)
3Non-linear optic crystal does not have symmetry centre, belongs to rhombic system, and spacer is Pna2
1, its unit cell parameters is:
α=β=γ=90 °.
Another object of the present invention is to provide a kind of K
3Al
2(PO
4)
3The non-linear optic crystal preparation method, it uses K
2O-P
2O
5Fusing assistant system, crystal can not cause having foreign ion to enter lattice in process of growth, product purity height, crystal are easily grown up and transparent nothing parcel, and it is very fast to have the speed of growth, and cost is low, obtains advantages such as large-size crystal easily; Obtained K
3Al
2(PO
4)
3Non-linear optic crystal has the transmission region than broad, and hardness is bigger, good mechanical property, and not easily broken and deliquescence is easy to advantages such as processing and preservation; The device for non-linear optical that the non-linear optic crystal that makes with the present invention is manufactured at room temperature, is made light source with the Nd:YAG Q-switched laser, and incident wavelength is the infrared light of 1064nm, and output wavelength is the green laser of 532nm, laser intensity and KDP (KH
2PO
4) quite.
Technical scheme of the present invention is as follows:
K provided by the invention
3Al
2(PO
4)
3Non-linear optic crystal, it does not have symmetry centre, belongs to rhombic system, and spacer is Pna2
1, its unit cell parameters is:
α=β=γ=90 °.
K provided by the invention
3Al
2(PO
4)
3The preparation method of non-linear optic crystal, it adopts the flux method growing crystal, and described fusing assistant is K
2O-P
2O
5The system fusing assistant, preparation process is as follows:
1) batching and pre-treatment:
With K
3Al
2(PO
4)
3Polycrystalline powder and solubility promoter be K in molar ratio
3Al
2(PO
4)
3: K
2O: P
2O
5The ratio of=1mol: 0.5-1.5mol: 0.5-1.5mol batching also mixes, and with the batching that the mixes opening platinum crucible of packing into, places retort furnace to be warming up to 1000-1050 ℃ of fusion 10-24 hour, cools off afterwards;
2) growing crystal:
The cooled crucible that above-mentioned batching is housed is placed vertical crystal growing furnace, rise to 1000-1050 ℃, constant temperature 24-48 hour, be cooled on the temperature of saturation 10-20 ℃ with 10-30 ℃ of/hour rate of temperature fall then with 50-100 ℃ of/hour temperature rise rate;
K is equipped with in the lower end
3Al
2(PO
4)
3The seed rod of seed crystal imports crystal growing furnace from crystal growing furnace top aperture, makes K
3Al
2(PO
4)
3Seed crystal contacts or stretches to molten surface among the liquation, after constant temperature 10-30 minute, is cooled to temperature of saturation with 5-20 ℃ of/hour rate of temperature fall;
Growing crystal in molten surface or liquation, with 0.1-3 ℃/day rate of temperature fall cooling growth, seed crystal is rotated with 0-50 rev/min of rotating speed in the crystal growing process; After treating that required yardstick is arrived in crystal growth, promote seed rod, make crystal break away from liquid level, and carry out aftertreatment, obtain transparent K
3Al
2(PO
4)
3Non-linear optic crystal.
Described aftertreatment is meant: the crystal of disengaging liquation liquid level is still stayed in the growth furnace and is annealed, and is cooled to room temperature with 20-100 ℃/hour rate of temperature fall.The best rate of temperature fall of its aftertreatment is 30-50 ℃/hour.
Described K
3Al
2(PO
4)
3The polycrystalline powder is by containing the K compound and containing the Al compound and contain P-compound and carry out high temperature solid state reaction and obtain: will contain the K compound, contain the Al compound and contain P-compound by wherein K: the molar ratio weighing batching of Al: P=3mol: 2mol: 6mol also mixes, the compacting in the platinum crucible of packing into afterwards, place retort furnace, be warming up to 200 ℃ with 30 ℃/hour, constant temperature 10 hours, take out sample after cooling and grind mixing again, place crucible and compacting again, in retort furnace, be warming up to 500 ℃ with 50 ℃/hour, sintering 24 hours takes out sample and grinds mixing again, places crucible and compacting again, in retort furnace in 700 ℃ of sintering 24 hours, sample is taken out, put into mortar and smash grinding to pieces, promptly get K
3Al
2(PO
4)
3The polycrystalline powder;
The described K of containing compound is for containing potassium oxide, salt of wormwood, saltpetre, potassium oxalate, potassiumphosphate or potassium hydroxide;
The described Al of containing compound is oxide compound aluminium, aluminium carbonate, aluminum nitrate, oxalic acid aluminium, aluminum phosphate or aluminium hydroxide;
The described P-compound that contains is P
2O
5, NH
4H
2PO
4, (NH
4)
2HPO
4Or (NH
4)
3PO
4
Described K
3Al
2(PO
4)
3The polycrystalline powder prepares by following reaction formula:
(1)3K
2CO
3+2Al
2O
3+6NH
4H
2PO
4＝2K
3Al
2(PO
4)
3+3CO
2↑+9H
2O↑+6NH
3↑
(2)3K
2O+2Al
2O
3+6NH
4H
2PO
4＝2K
3Al
2(PO
4)
3+9H
2O↑+6NH
3↑
(3)12KNO
3+4Al
2O
3+12NH
4H
2PO
4＝4K
3Al
2(PO
4)
3+18H
2O↑+12NO
2↑+3O
2↑+12NH
3↑
(4)3KOH+Al
2O
3+3NH
4H
2PO
4＝K
3Al
2(PO
4)
3+6H
2O↑+3NH
3↑
(5)3K
2O+2Al
2O
3+3P
2O
5＝2K
3Al
2(PO
4)
3
(6)3K
2O+4Al(OH)
3+6NH
4H
2PO
4＝2K
3Al
2(PO
4)
3+15H
2O↑+6NH
3↑
(7)3K
2O+4Al(NO
3)
3+3P
2O
5＝2K
3Al
2(PO
4)
3+4NO
2↑+O
2↑
(8)3K
2CO
3+4Al(OH)
3+6NH
4H
2PO
4＝2K
3Al
2(PO
4)
3+3CO
2↑+15H
2O↑+6NH
3↑
(9)3K
2CO
3+4Al(NO
3)
3+6NH
4H
2PO
4＝
2K
3Al
2(PO
4)
3+3CO
2↑+9H
2O↑+4NO
2↑+O
2↑+6NH
3↑。
Can with the logical light mirror polish of crystal, promptly can be used as device for non-linear optical and use by required angle, thickness and sectional dimension sliced crystal.K provided by the invention
3Al
2(PO
4)
3The purposes of non-linear optic crystal, it is used to prepare device for non-linear optical; Prepared device for non-linear optical comprises a branch of at least incidence electromagnetic radiation by at least one this K
3Al
2(PO
4)
3Produce the device that a branch of at least frequency is different from the output radiation of incidence electromagnetic radiation behind the non-linear optic crystal.The K of the inventive method preparation
3Al
2(PO
4)
3Non-linear optic crystal does not have symmetry centre, belongs to rhombic system, and spacer is Pna2
1, its unit cell parameters is:
α=β=γ=90 °.It is stable to have physical and chemical performance, and hardness is bigger, and good mechanical property is not easily broken, is difficult for deliquescence, is easy to advantages such as processing and preservation; Differential thermal analysis records K
3Al
2(PO
4)
3Fusing point is 1183 ℃, and this crystal is 40-80% in the transmitance of 180-2500nm scope, crystalline powder frequency-doubled effect and KDP (KH
2PO
4) quite.
Effect of the present invention is as follows:
K provided by the invention
3Al
2(PO
4)
3The non-linear optic crystal preparation method has used K
2O-P
2O
5Fusing assistant system, crystal can not cause having foreign ion to enter lattice in process of growth, product purity height, crystal are easily grown up and transparent nothing parcel, have fast growth, and cost is low, obtains advantages such as large-size crystal easily; Obtained K
3Al
2(PO
4)
3Non-linear optic crystal has the transmission region than broad, and hardness is bigger, good mechanical property, and not easily broken and deliquescence is easy to advantages such as processing and preservation; The device for non-linear optical that the non-linear optic crystal that makes with the present invention is manufactured at room temperature, is made light source with the Nd:YAG Q-switched laser, and incident wavelength is the infrared light of 1064nm, and output wavelength is the green laser of 532nm, laser intensity and KDP (KH
2PO
4) quite.
Description of drawings
Fig. 1 is the K with the inventive method preparation
3Al
2(PO
4)
3The fundamental diagram of a kind of typical nonlinear optics that non-linear optic crystal is manufactured, wherein: 1 is laser apparatus, and 2 is incoming laser beam, and 3 is the K through aftertreatment and optics processing
3Al
2(PO
4)
3Single crystal, 4 is the outgoing laser beam that is produced, 5 is filter plate; Described 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 laser beam 2 is that wavelength is the infrared light of 1064nm, passes through K
3Al
2(PO
4)
3It is the green frequency doubled light of 532nm that monocrystalline produces wavelength, and it is the infrared light of 1064nm and the green glow of 532nm that outgoing laser beam 4 contains wavelength, and the effect of filter plate 5 is elimination infrared light compositions, only allows green frequency doubled light to pass through.
Embodiment
Press reaction formula (2): 3K
2O+2Al
2O
3+ 6NH
4H
2PO
4=2K
3Al
2(PO
4)
3+ 9H
2O ↑+6NH
3↑
Take by weighing 12.42gK
2O, 6.12gAl
2O
3And 20.70gNH
4H
2PO
4(K
2O: Al
2O
3: NH
4H
2PO
4=0.09mol: 0.06mol: 0.18mol), the raw material that takes by weighing is put into mortar, mix and careful the grinding, pack into then in the opening platinum crucible of Φ 60mm * 60mm,, put into retort furnace its compacting, be warming up to 200 ℃ with 30 ℃/hour, constant temperature 10 hours takes out after cooling, and this moment, sample was more loose; Take out sample and grind mixing again, place crucible and compacting again, in retort furnace, be warming up to 500 ℃ with 50 ℃/hour, sintering 24 hours, this moment, sample was shrunk to piece; Take out sample and grind mixing again, place crucible and compacting again, in retort furnace,, sample is taken out, put into mortar and smash grinding to pieces, promptly get K in 700 ℃ of sintering 24 hours
3Al
2(PO
4)
3The polycrystalline powder.
Embodiment 2: flux method prepares K
3Al
2(PO
4)
3Non-linear optic crystal.
Take by weighing 55.2 gram K
2CO
3, 20.2 the gram Al
2O
3With 92.0 gram NH
4H
2PO
4[K
3Al
2(PO
4)
3: K
2O: P
2O
5=1mol: 0.5mol: 0.5mol] behind the raw material uniform mixing, pack in the opening platinum crucible of Φ 80mm * 60mm, place retort furnace, rise to 700 ℃ with 30 ℃/hour, constant temperature 24 hours, take out after cooling, put into mortar and smash to pieces, be fused under 1050 ℃ in the retort furnace in the opening platinum crucible of Φ 60mm * 60mm in batches; The cooling back is put into the vertical monocrystal growing furnace to this crucible, with lagging material the opening that is positioned at vertical monocrystal growing furnace top is sealed up, stay an aperture that can supply seed rod to come in and go out in vertical monocrystal growing furnace furnace roof portion and corresponding position, crucible central position, be warming up to 1050 ℃ with 50 ℃/hour, behind the constant temperature 48 hours, be cooled to 950 ℃ with 30 ℃/hour; With K
3Al
2(PO
4)
3Seed crystal is fixed on the seed rod lower end with platinum filament, from growth furnace top aperture seed crystal is imported crucible, and seed crystal is contacted with liquid level, seed crystal rotates with 20 rev/mins speed, behind the constant temperature 30 minutes, be cooled to 940 ℃ with 10 ℃/hour, then with 0.2 ℃/day speed cooling growth; After treating that crystal growth finishes, make crystal break away from liquid level, reduce to room temperature, obtain to be of a size of the transparent K of 12mm * 6mm * 3mm with 30 ℃ of/hour speed
3Al
2(PO
4)
3Crystal.
Embodiment 3: flux method prepares K
3Al
2(PO
4)
3Non-linear optic crystal
With synthetic K
3Al
2(PO
4)
3Polycrystal powder (embodiment 1 products therefrom) is a raw material, analytical pure K
2CO
3And NH
4H
2PO
4Make fusing assistant, take by weighing 47.6 gram K
3Al
2(PO
4)
3Powder, 6.9 gram K
2CO
3, 34.5 the gram NH
4H
2PO
4[be equivalent to K
3Al
2(PO
4)
3: K
2O: P
2O
5=1mol: 0.5mol: 1.5mol], behind the uniform mixing, be fused under 1030 ℃ in the retort furnace in the opening platinum crucible of Φ 60mm * 60mm in batches; The cooling back is put into the vertical monocrystal growing furnace to this crucible, with lagging material the opening that is positioned at furnace roof portion is sealed up, stay an aperture that can supply seed rod to come in and go out in furnace roof portion and corresponding position, crucible central position, be warming up to 1030 ℃ with 80 ℃/hour, behind the constant temperature 24 hours, be cooled to 945 ℃ with 20 ℃/hour, with K
3Al
2(PO
4)
3Seed crystal is fixed on the seed rod lower end with platinum filament, from furnace roof portion aperture seed crystal is imported crucible, makes it to contact with liquid level, and seed crystal is with the rotation of 30 rev/mins speed, and constant temperature is after 20 minutes, is cooled to 930 ℃ with 20 ℃/hour, then with 1.5 ℃/day speed cooling growth.After treating that crystal growth finishes, make crystal break away from liquid level, reduce to room temperature, obtain the transparent K of centimetre-sized with 40 ℃ of/hour speed
3Al
2(PO
4)
3Crystal.
Embodiment 4: flux method prepares K
3Al
2(PO
4)
3Non-linear optic crystal
With synthetic K
3Al
2(PO
4)
3Powder (embodiment 1 products therefrom) is a raw material, analytical pure K
2CO
3, NH
4H
2PO
4Make fusing assistant, take by weighing the K of 47.6 grams
3Al
2(PO
4)
3The K of powder, 20.7 grams
2CO
3, the NH of 11.5 grams
4H
2PO
4[K
3Al
2(PO
4)
3: K
2O: P
2O
5=1mol: 1.5mol: 0.5mol], behind the uniform mixing, be fused under 1000 ℃ in the retort furnace in the opening platinum crucible of Φ 60mm * 60mm in batches; The cooling back is put into the vertical monocrystal growing furnace to this crucible, with lagging material the opening that is positioned at furnace roof portion is sealed up, stay an aperture that can supply seed rod to come in and go out in furnace roof portion and corresponding position, crucible central position, be warming up to 1000 ℃ with 100 ℃/hour, behind the constant temperature 36 hours, be cooled to 930 ℃ with 10 ℃/hour, with K
3Al
2(PO
4)
3Seed crystal is fixed on the seed rod lower end with platinum filament, from furnace roof portion aperture seed crystal is imported crucible, makes it to be immersed in fully in the melt, seed crystal rotates with 50 rev/mins speed, behind the constant temperature 10 minutes, be cooled to 910 ℃ with 15 ℃/hour, then with 1 ℃/day speed cooling growth.After treating that crystal growth finishes, make crystal break away from liquid level, reduce to room temperature, obtain the transparent K of centimetre-sized with 50 ℃ of/hour speed
3Al
2(PO
4)
3Crystal.
Embodiment 5: flux method prepares K
3Al
2(PO
4)
3Non-linear optic crystal
Take by weighing 69.0 gram K
2CO
3, 20.2 gram Al
2O
3, 115.0 gram NH
4H
2PO
4Raw material [K
3Al
2(PO
4)
3: K
2O: P
2O
5=1mol: 1mol: 1mol], behind the uniform mixing, pack in the opening platinum crucible of Φ 80mm * 60mm, place retort furnace, rise to 700 ℃, constant temperature 24 hours, taking-up after cooling with 30 ℃/hour, put into mortar and smash to pieces, be fused under 1000 ℃ in the retort furnace in the opening platinum crucible of Φ 60mm * 60mm in batches; The cooling back is put into the vertical monocrystal growing furnace to this crucible, with lagging material the opening that is positioned at furnace roof portion is sealed up, stay an aperture that can supply seed rod to come in and go out in furnace roof portion and corresponding position, crucible central position, be warming up to 1000 ℃ with 50 ℃/hour, behind the constant temperature 30 hours, be cooled to 930 ℃ with 20 ℃/hour, with K
3Al
2(PO
4)
3Seed crystal is fixed on the seed rod lower end with platinum filament, from furnace roof portion aperture seed crystal is imported crucible, makes it to contact with liquid level, and seed crystal is with the rotation of 20 rev/mins speed, and constant temperature is after 30 minutes, is cooled to 920 ℃ with 10 ℃/hour, then with 1.5 ℃/day speed cooling growth.After treating that crystal growth finishes, make crystal break away from liquid level, reduce to room temperature, obtain to be of a size of the transparent K of 8mm * 5mm * 3mm with 30 ℃ of/hour speed
3Al
2(PO
4)
3Crystal.
Embodiment 6: flux method prepares K
3Al
2(PO
4)
3Non-linear optic crystal
Take by weighing 82.8 gram K
2CO
3, 20.2 gram Al
2O
3, 138.0 gram NH
4H
2PO
4Raw material [K
3Al
2(PO
4)
3: K
2O: P
2O
5=1mol: 1.5mol: 1.5mol], behind the uniform mixing, pack in the opening platinum crucible of Φ 80mm * 60mm, place retort furnace, rise to 700 ℃, constant temperature 24 hours, taking-up after cooling with 40 ℃/hour, put into mortar and smash to pieces, be fused under 1000 ℃ in the retort furnace in the opening platinum crucible of Φ 60mm * 60mm in batches; The cooling back is put into the vertical monocrystal growing furnace to this crucible, with lagging material the opening that is positioned at furnace roof portion is sealed up, stay an aperture that can supply seed rod to come in and go out in furnace roof portion and corresponding position, crucible central position, be warming up to 1000 ℃ with 60 ℃/hour, behind the constant temperature 24 hours, be cooled to 910 ℃ with 30 ℃/hour, with K
3Al
2(PO
4)
3Seed crystal is fixed on the seed rod lower end with platinum filament, from furnace roof portion aperture seed crystal is imported crucible, makes it to be immersed in fully in the melt, seed crystal rotates with 20 rev/mins speed, behind the constant temperature 20 minutes, be cooled to 900 ℃ with 15 ℃/hour, then with 2.5 ℃/day speed cooling growth.After treating that crystal growth finishes, make crystal break away from liquid level, reduce to room temperature, obtain to be of a size of the transparent K of 10mm * 5mm * 3mm with 30 ℃ of/hour speed
3Al
2(PO
4)
3Crystal.
Embodiment 7:
K with embodiment 2 gained
3Al
2(PO
4)
3Non-linear optic crystal is done to see through spectrometry, and this crystal is transparent in 180nm to 2500nm wavelength region; Not easily broken, be easy to cutting, polishing processing and preservation, not deliquescence.With K
3Al
2(PO
4)
3Crystal is pressed accompanying drawing 1 shown device side in 3 position, and at room temperature, with transferring Q Nd:YAG laser apparatus to make light source, incident wavelength is the infrared light of 1064nm, and output wavelength is the green laser of 532nm, and laser intensity and KDP are suitable.
Claims (7)
1. K
3Al
2(PO
4)
3Non-linear optic crystal, it does not have symmetry centre, belongs to rhombic system, and spacer is Pna2
1, its unit cell parameters is:
α=β=γ=90 °.
2. described K of claim 1
3Al
2(PO
4)
3The preparation method of non-linear optic crystal, it adopts the flux method growing crystal, and described fusing assistant is K
2O-P
2O
5The system fusing assistant, preparation process is as follows:
1) batching and pre-treatment:
With K
3Al
2(PO
4)
3Polycrystalline powder and solubility promoter be K in molar ratio
3Al
2(PO
4)
3: K
2O: P
2O
5The ratio of=1mol: 0.5-1.5mol: 0.5-1.5mol batching also mixes, and with the batching that the mixes opening platinum crucible of packing into, places retort furnace to be warming up to 1000-1050 ℃ of fusion 10-24 hour, cools off afterwards;
2) growing crystal:
The cooled crucible that above-mentioned batching is housed is placed vertical crystal growing furnace, rise to 1000-1050 ℃, constant temperature 24-48 hour, be cooled on the temperature of saturation 10-20 ℃ with 10-30 ℃ of/hour rate of temperature fall then with 50-100 ℃ of/hour temperature rise rate;
K is equipped with in the lower end
3Al
2(PO
4)
3The seed rod of seed crystal imports crystal growing furnace from crystal growing furnace top aperture, makes K
3Al
2(PO
4)
3Seed crystal after constant temperature 10-30 minute, is cooled to temperature of saturation with 5-20 ℃ of/hour rate of temperature fall with among the liquation liquid level contacts or stretch to liquation;
Growing crystal in molten surface or liquation, with 0.1-3 ℃/day rate of temperature fall cooling growth, seed crystal is rotated with 0-50 rev/min of rotating speed in the crystal growing process; After treating that required yardstick is arrived in crystal growth, promote seed rod, make crystal break away from liquid level, and carry out aftertreatment, obtain transparent K
3Al
2(PO
4)
3Non-linear optic crystal.
3. by the described K of claim 2
3Al
2(PO
4)
3The preparation method of non-linear optic crystal is characterized in that, described aftertreatment is meant: the crystal of disengaging liquation liquid level is still stayed in the growth furnace and is annealed, and is cooled to room temperature with 20-100 ℃/hour rate of temperature fall.
4. by the described K of claim 4
3Al
2(PO
4)
3The preparation method of non-linear optic crystal is characterized in that, the rate of temperature fall of described aftertreatment is 30-50 ℃/hour.
5. by the described K of claim 2
3Al
2(PO
4)
3The preparation method of non-linear optic crystal is characterized in that, described K
3Al
2(PO
4)
3The polycrystalline powder is by containing the K compound and containing the Al compound and contain P-compound and carry out high temperature solid state reaction and obtain: will contain the K compound, contain the Al compound and contain P-compound by wherein K: the molar ratio weighing batching of Al: P=3mol: 2mol: 6mol also mixes, the compacting in the platinum crucible of packing into afterwards, place retort furnace, be warming up to 200 ℃ with 30 ℃/hour, constant temperature 10 hours, take out sample after cooling and grind mixing again, place crucible and compacting again, in retort furnace, be warming up to 500 ℃ with 50 ℃/hour, sintering 24 hours takes out sample and grinds mixing again, places crucible and compacting again, in retort furnace in 700 ℃ of sintering 24 hours, sample is taken out, put into mortar and smash grinding to pieces, promptly get K
3Al
2(PO
4)
3The polycrystalline powder;
The described K of containing compound is for containing potassium oxide, salt of wormwood, saltpetre, potassium oxalate, potassiumphosphate or potassium hydroxide;
The described Al of containing compound is oxide compound aluminium, aluminium carbonate, aluminum nitrate, oxalic acid aluminium, aluminum phosphate or aluminium hydroxide;
The described P-compound that contains is P
2O
5, NH
4H
2PO
4, (NH
4)
2HPO
4Or (NH
4)
3PO
4
6. by the described K of claim 2
3Al
2(PO
4)
3The preparation method of non-linear optic crystal is characterized in that, described K
3Al
2(PO
4)
3The polycrystalline powder prepares by following reaction formula:
(1)3K
2CO
3+2Al
2O
3+6NH
4H
2PO
4＝2K
3Al
2(PO
4)
3+3CO
2↑+9H
2O↑+6NH
3↑
(2)3K
2O+2Al
2O
3+6NH
4H
2PO
4＝2K
3Al
2(PO
4)
3+9H
2O↑+6NH
3↑
(3)12KNO
3+4Al
2O
3+12NH
4H
2PO
4＝4K
3Al
2(PO
4)
3+18H
2O↑+12NO
2↑+3O
2↑+12NH
3↑
(4)3KOH+Al
2O
3+3NH
4H
2PO
4＝K
3Al
2(PO
4)
3+6H
2O↑+3NH
3↑
(5)3K
2O+2Al
2O
3+3P
2O
5＝2K
3Al
2(PO
4)
3
(6)3K
2O+4Al(OH)
3+6NH
4H
2PO
4＝2K
3Al
2(PO
4)
3+15H
2O↑+6NH
3↑
(7)3K
2O+4Al(NO
3)
3+3P
2O
5＝2K
3Al
2(PO
4)
3+4NO
2↑+O
2↑
(8)3K
2CO
3+4Al(OH)
3+6NH
4H
2PO
4＝2K
3Al
2(PO
4)
3+3CO
2↑+15H
2O↑+6NH
3↑
(9)3K
2CO
3+4Al(NO
3)
3+6NH
4H
2PO
4＝
2K
3Al
2(PO
4)
3+3CO
2↑+9H
2O↑+4NO
2↑+O
2↑+6NH
3↑。
7. press the described K of claim 2 for one kind
3Al
2(PO
4)
3The purposes of non-linear optic crystal, it is used to prepare device for non-linear optical; Prepared device for non-linear optical comprises a branch of at least incidence electromagnetic radiation by at least one this K
3Al
2(PO
4)
3Produce the device that a branch of at least frequency is different from the output radiation of incidence electromagnetic radiation behind the non-linear optic crystal.
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