CN103741217A - Sodium yttrium borate, sodium yttrium borate nonlinear optical crystal, preparation method and application - Google Patents
Sodium yttrium borate, sodium yttrium borate nonlinear optical crystal, preparation method and application Download PDFInfo
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- CN103741217A CN103741217A CN201410025036.5A CN201410025036A CN103741217A CN 103741217 A CN103741217 A CN 103741217A CN 201410025036 A CN201410025036 A CN 201410025036A CN 103741217 A CN103741217 A CN 103741217A
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- yttrium
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- 239000013078 crystal Substances 0.000 title claims abstract description 105
- 230000003287 optical effect Effects 0.000 title claims abstract description 28
- 238000002360 preparation method Methods 0.000 title claims abstract description 21
- NPVZNWLMRQBDQL-UHFFFAOYSA-N B([O-])([O-])[O-].[Y+3].[Na+] Chemical compound B([O-])([O-])[O-].[Y+3].[Na+] NPVZNWLMRQBDQL-UHFFFAOYSA-N 0.000 title claims description 35
- 150000001875 compounds Chemical class 0.000 claims abstract description 25
- 238000000034 method Methods 0.000 claims abstract description 23
- 238000003786 synthesis reaction Methods 0.000 claims abstract description 3
- 239000011734 sodium Substances 0.000 claims description 95
- 238000001816 cooling Methods 0.000 claims description 25
- 230000004907 flux Effects 0.000 claims description 19
- 239000004570 mortar (masonry) Substances 0.000 claims description 16
- 239000007788 liquid Substances 0.000 claims description 15
- 239000000203 mixture Substances 0.000 claims description 13
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 12
- 239000000126 substance Substances 0.000 claims description 12
- 239000000956 alloy Substances 0.000 claims description 10
- 229910045601 alloy Inorganic materials 0.000 claims description 10
- 238000005245 sintering Methods 0.000 claims description 9
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 8
- VWDWKYIASSYTQR-UHFFFAOYSA-N sodium nitrate Chemical compound [Na+].[O-][N+]([O-])=O VWDWKYIASSYTQR-UHFFFAOYSA-N 0.000 claims description 8
- 238000003756 stirring Methods 0.000 claims description 8
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 4
- 230000005670 electromagnetic radiation Effects 0.000 claims description 4
- IBSDADOZMZEYKD-UHFFFAOYSA-H oxalate;yttrium(3+) Chemical compound [Y+3].[Y+3].[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O IBSDADOZMZEYKD-UHFFFAOYSA-H 0.000 claims description 4
- SIWVEOZUMHYXCS-UHFFFAOYSA-N oxo(oxoyttriooxy)yttrium Chemical compound O=[Y]O[Y]=O SIWVEOZUMHYXCS-UHFFFAOYSA-N 0.000 claims description 4
- 238000002203 pretreatment Methods 0.000 claims description 4
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 4
- 229940001593 sodium carbonate Drugs 0.000 claims description 4
- 229940083608 sodium hydroxide Drugs 0.000 claims description 4
- 239000004317 sodium nitrate Substances 0.000 claims description 4
- 229940001516 sodium nitrate Drugs 0.000 claims description 4
- 235000010344 sodium nitrate Nutrition 0.000 claims description 4
- ZNCPFRVNHGOPAG-UHFFFAOYSA-L sodium oxalate Chemical compound [Na+].[Na+].[O-]C(=O)C([O-])=O ZNCPFRVNHGOPAG-UHFFFAOYSA-L 0.000 claims description 4
- 229940039790 sodium oxalate Drugs 0.000 claims description 4
- KKCBUQHMOMHUOY-UHFFFAOYSA-N sodium oxide Chemical compound [O-2].[Na+].[Na+] KKCBUQHMOMHUOY-UHFFFAOYSA-N 0.000 claims description 4
- 229910001948 sodium oxide Inorganic materials 0.000 claims description 4
- QVOIJBIQBYRBCF-UHFFFAOYSA-H yttrium(3+);tricarbonate Chemical compound [Y+3].[Y+3].[O-]C([O-])=O.[O-]C([O-])=O.[O-]C([O-])=O QVOIJBIQBYRBCF-UHFFFAOYSA-H 0.000 claims description 4
- DEXZEPDUSNRVTN-UHFFFAOYSA-K yttrium(3+);trihydroxide Chemical compound [OH-].[OH-].[OH-].[Y+3] DEXZEPDUSNRVTN-UHFFFAOYSA-K 0.000 claims description 4
- BXJPTTGFESFXJU-UHFFFAOYSA-N yttrium(3+);trinitrate Chemical compound [Y+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O BXJPTTGFESFXJU-UHFFFAOYSA-N 0.000 claims description 4
- 230000005855 radiation Effects 0.000 claims description 3
- 125000006850 spacer group Chemical group 0.000 claims description 3
- 230000002457 bidirectional effect Effects 0.000 claims description 2
- 229910052796 boron Inorganic materials 0.000 claims description 2
- 230000007246 mechanism Effects 0.000 claims description 2
- 238000006243 chemical reaction Methods 0.000 abstract description 10
- 230000008569 process Effects 0.000 abstract description 3
- 230000005540 biological transmission Effects 0.000 abstract 1
- 238000004519 manufacturing process Methods 0.000 abstract 1
- 150000003839 salts Chemical class 0.000 abstract 1
- 238000010792 warming Methods 0.000 description 14
- 239000000463 material Substances 0.000 description 9
- 239000002994 raw material Substances 0.000 description 9
- 239000003153 chemical reaction reagent Substances 0.000 description 8
- 239000007787 solid Substances 0.000 description 7
- 239000000843 powder Substances 0.000 description 6
- 230000000694 effects Effects 0.000 description 5
- 238000000227 grinding Methods 0.000 description 4
- 238000009413 insulation Methods 0.000 description 4
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 4
- 229910019655 synthetic inorganic crystalline material Inorganic materials 0.000 description 4
- -1 rare earth ion Chemical class 0.000 description 3
- 229910052761 rare earth metal Inorganic materials 0.000 description 3
- 229910052688 Gadolinium Inorganic materials 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- 229910052746 lanthanum Inorganic materials 0.000 description 2
- 229910052697 platinum Inorganic materials 0.000 description 2
- 239000010453 quartz Substances 0.000 description 2
- 229910052727 yttrium Inorganic materials 0.000 description 2
- BTBUEUYNUDRHOZ-UHFFFAOYSA-N Borate Chemical compound [O-]B([O-])[O-] BTBUEUYNUDRHOZ-UHFFFAOYSA-N 0.000 description 1
- 229910052691 Erbium Inorganic materials 0.000 description 1
- 229910052765 Lutetium Inorganic materials 0.000 description 1
- 229910052772 Samarium Inorganic materials 0.000 description 1
- 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
- 239000002178 crystalline material Substances 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 238000003199 nucleic acid amplification method Methods 0.000 description 1
- 238000004321 preservation Methods 0.000 description 1
- 150000002910 rare earth metals Chemical class 0.000 description 1
- 230000003595 spectral effect Effects 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 238000002834 transmittance Methods 0.000 description 1
- 229910019901 yttrium aluminum garnet Inorganic materials 0.000 description 1
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Abstract
Na3Y3(BO3)4Compound, Na3Y3(BO3)4Nonlinear optical crystal and its preparation method and application; the compound is prepared by a chemical synthesis method; the crystal is prepared by a molten salt method; prepared Na3Y3(BO3)4The crystal has larger nonlinear optical effect and wide transmission range,the laser has good mechanical property, is not deliquescent, is easy to process and store, meets the requirement of frequency conversion of blue-green light band laser, can be used for manufacturing a nonlinear optical device, uses an Nd-YAG Q-switched laser as a light source at room temperature, inputs infrared light with the wavelength of 1064nm, outputs green laser with the wavelength of 532nm, and has the laser intensity of 2-4 times KDP.
Description
Technical field
The invention belongs to compound, crystal and preparation and Application Areas, particularly a kind of yttrium borate sodium Na
3y
3(BO
3)
4compound, Na
3y
3(BO
3)
4non-linear optic crystal and preparation method and purposes.
Technical background
Various new effects, the new phenomenon occurring in research intense laser radiation and matter interaction process and the subject that utilizes the application of these effects and phenomenon, be called nonlinear optics.The crystal with non-linear optical effect is referred to as non-linear optic crystal.Here non-linear optical effect refers to laser freuqency doubling and frequency, difference frequency, optical parameter amplification etc.But this can only just may realize at non-centrosymmetrical crystal.Utilize the nonlinear optical effects of crystal can make the device for non-linear optical such as harmonic generator, photoparametric amplifier, be widely applied to the major areas that concerns national economy now.Laser can be realized frequency inverted by device for non-linear optical, thereby widens the wavelength region of laser apparatus, makes laser obtain applying more widely.All solid state bluish-green laser system is to produce near infrared laser by solid laser, carries out frequency inverted realize green and blue light output through non-linear optic crystal, at laser technology field, has broad application prospects.
RE(rare earth) borate non-linear optic crystal, due to electronics layout character, sees through scope large, and ultraviolet cut-on limit is little, and non-linear optical effect is large, is the nonlinear optical material of a class excellence.And structure is very close with chemical property between rare earth ion, can easily realize doping vario-property, thereby realize self-frequency-doubling laser output.This class material of having found has YAl
3(BO
3)
4(referring to Soviet Union magazine < < Kristall und Technik > > Vol.9,63,1974), Ca
4reO (BO
3)
3(Re=La, Gd, Sm, Er, Y, Lu) (referring to USA Magazine < < Chemistry Material > > Vol.4,737,1992) and R
2mB
10o
19(R=Ca, Sr, Ba; The rare earth ions such as M=Y, La, Gd) (referring to Chinese invention patent application prospectus, publication number CN1236027A, United States Patent (USP) 6,146,553) etc.These materials have large optical transmittance, and larger non-linear optical effect can be used for making the device for non-linear optical of bluish-green wave band.Because non-linear optic crystal is relevant with the non-linear optical effect size of crystal to the effciency of energy transfer of incident laser, for improving the output rating of all solid state blue green light laser system, be necessary to find the crystalline material that non-linear optical effect is larger.
Summary of the invention
The object of the present invention is to provide a kind of yttrium borate sodium compound and preparation method thereof, the chemical formula of this yttrium borate sodium compound is Na
3y
3(BO
3)
4; Another object of the present invention is to provide a kind of yttrium borate sodium non-linear optic crystal and growth method, this yttrium borate sodium non-linear optic crystal belongs to hexagonal system, spacer P6
3mc, its powder frequency doubling intensity is 2～4 times of KDP (KH
2pO
4); A further object of the present invention is the purposes for the preparation of device for non-linear optical of this yttrium borate sodium non-linear optic crystal.
Technical scheme of the present invention is as follows:
Yttrium borate sodium compound provided by the invention, its chemical formula is Na
3y
3(BO
3)
4.
The preparation method of yttrium borate sodium compound provided by the invention, it adopts chemical synthesis preparation: will be containing Na compound, contain after Y compound and boride alloy mix and pack crucible compacting into, be placed in retort furnace and be warmed up to 500 ℃ of sintering 24～48h with the temperature rise rate of 20 ℃/h～50 ℃/h, again grind evenly after cooling, again pack crucible and compacting into and be placed in retort furnace in 800～1100 ℃ of sintering 24～72h, obtain yttrium borate sodium compound, its chemical formula is Na
3y
3(BO
3)
4;
Described is 3:3:4 containing Na compound, containing the mol ratio of contained Na, Y and B in Y compound and the mixed uniformly mixture of boride alloy;
Described is sodium oxide, sodium carbonate, SODIUMNITRATE, sodium oxalate or sodium hydroxide containing Na compound;
Described is yttrium oxide, yttrium carbonate, Yttrium trinitrate, yttrium oxalate or yttrium hydroxide containing Y compound;
Described boride alloy is H
3bO
3or B
2o
3.
Can obtain chemical formula by following reaction formula is Na
3y
3(BO
3)
4compound:
（1）3Na
2CO
3+3Y
2O
3+8H
3BO
3=2Na
3Y
3(BO
3)
4+3CO
2↑+12H
2O↑
（2）6Na
2C
2O
4+6Y
2O
3+16H
3BO
3=4Na
3Y
3(BO
3)
4+12CO↑+24H
2O↑+3O
2↑
（3）3Na
2O+3Y
2O
3+8H
3BO
3=2Na
3Y
3(BO
3)
4+12H
2O↑
（4）12NaNO
3+6Y
2O
3+16H
3BO
3=4Na
3Y
3(BO
3)
4+12NO
2↑+24H
2O↑+3O
2↑
（5）6NaOH+3Y
2O
3+8H
3BO
3=2Na
3Y
3(BO
3)
4+15H
2O↑
（6）3Na
2O+3Y
2O
3+4B
2O
3=2Na
3Y
3(BO
3)
4
（7）3Na
2O+6Y(NO
3)
3+4B
2O
3=2Na
3Y
3(BO
3)
4+18NO
2↑
（8）3Na
2O+3Y
2(CO
3)
3+8H
3BO
3=2Na
3Y
3(BO
3)
4+12H
2O↑+9CO
2↑
（9）3Na
2CO
3+3Y
2(CO
3)
3+8H
3BO
3=2Na
3Y
3(BO
3)
4+12H
2O↑+12CO
2↑
Yttrium borate sodium non-linear optic crystal provided by the invention, its chemical formula is Na
3y
3(BO
3)
4; This crystal does not have symmetry centre, belongs to hexagonal system, and spacer is P6
3mc (No.186), unit cell parameters is: a=10.1136 (14)
b=10.1136 (14)
c=6.7485 (13)
α=β=90 °, γ=120 °, Z=2, V=597.79 (2)
density is 3.172g/cm
3.
The growth method of yttrium borate sodium non-linear optic crystal provided by the invention, it adopts fusing assistant molten-salt growth, its growth step is as follows: using yttrium borate sodium compound as solute, fusing assistant is as flux, the abundant ground and mixed of ratio that by solute and flux is in molar ratio 1～10:1～30 in agate mortar is even, is packed into crucible and compacting and puts into retort furnace and carry out pre-treatment; Again pretreated mixture is melted in growth crucible in batches, growth crucible is placed in to crystal growing furnace and is heated to the liquation of mixture melt; And constant temperature stirs 24～72h, use and attempt seed crystal and record the temperature of saturation of system, more than temperature of saturation 10～30 ℃, the seed crystal being contained on seed rod is stretched in molten surface or liquation, and starting the rotating mechanism on seed rod, the speed of rotation of seed rod is 0～40 rev/min; In 30min, be cooled to temperature of saturation, after constant temperature 24h, with the speed cooling growing crystal of 0.2～2 ℃/day; The sense of rotation of seed rod is the bidirectional rotation that clockwise direction, counter clockwise direction or clockwise direction and counter clockwise direction hocket; After crystal grows into required yardstick, promote seed rod, make seed crystal depart from liquation liquid level; Crystal is stayed in growth furnace and is annealed, and with the speed that is not more than 50 ℃/h, is cooled to room temperature, obtains yttrium borate sodium non-linear optic crystal, and its chemical formula is Na
3y
3(BO
3)
4;
Described fusing assistant is Na
2cO
3-H
3bO
3-NaF system fusing assistant or Na
2cO
3-H
3bO
3system fusing assistant;
Described Na
2cO
3-H
3bO
3na in-NaF system fusing assistant
2cO
3: H
3bO
3: NaF mol ratio is 0～1.5:0～1.5:1～2; Described Na
2cO
3-H
3bO
3na in system fusing assistant
2cO
3: H
3bO
3mol ratio is 1:1.
Described pre-treatment refers to the solute and the flux mixture that fully grind is packed in crucible and be placed in retort furnace, with the temperature rise rate of 20～50 ℃/h, is warmed up to 500 ℃ of sintering 24～48h.
Described yttrium borate sodium compound solute is by containing Na compound, being the mixture replacing that 3:3:4 ratio forms containing Y compound and boride alloy in Na:Y:B mol ratio wherein;
Described is sodium oxide, sodium carbonate, SODIUMNITRATE, sodium oxalate or sodium hydroxide containing Na compound;
Described is yttrium oxide, yttrium carbonate, Yttrium trinitrate, yttrium oxalate or yttrium hydroxide containing Y compound;
Described boride alloy is H
3bO
3or B
2o
3.
The purposes of yttrium borate sodium non-linear optic crystal provided by the invention, this yttrium borate sodium non-linear optic crystal is for the preparation of device for non-linear optical, and described device for non-linear optical comprises at least a branch of incidence electromagnetic radiation is produced to the device that at least a branch of frequency is different from the output radiation of incidence electromagnetic radiation after by least one block of yttrium borate sodium non-linear optic crystal.
Effect of the present invention is: the invention provides a kind of chemical formula is Na
3y
3(BO
3)
4compound and preparation and the purposes of non-linear optic crystal and they; Adopt Na
2cO
3-H
3bO
3-NaF or Na
2cO
3-H
3bO
3fusing assistant system this crystal of growing, has product purity high, is difficult for mixing impurity, low cost and other advantages; The Na that obtains
3y
3(BO
3)
4it is stable that non-linear optic crystal has physical and chemical performance, and not deliquescence is easy to processing and preservation and the wide scope that sees through, and its ultraviolet cut-on limit is about 190nm, and powder SHG effect intensity is 2～4 times of KDP (KH
2pO
4); Non-linear optic crystal of the present invention can be used for making device for non-linear optical, at room temperature, uses Nd:YAG Q-switched laser as light source, the infrared light that incident wavelength is 1064nm, and the green laser that output wavelength is 532nm, laser intensity is 2～4 times of KDP (KH
2pO
4).
Accompanying drawing explanation
Fig. 1 uses Na
3y
3(BO
3)
4the fundamental diagram of a kind of typical device for non-linear optical that crystal is made;
Fig. 2 is yttrium borate sodium polycrystal powder X ray diffracting spectrum of the present invention;
Fig. 3 is yttrium borate sodium crystal structure iron of the present invention;
Wherein:
The Na of 1-laser apparatus 2-incoming laser beam 3-after cutting and optics processing
3y
3(BO
3)
4crystal
The laser beam 5-filter plate that 4-produces
Embodiment
Below in conjunction with drawings and Examples, further describe the present invention.
Embodiment 1: prepare Powdered Na
3y
3(BO
3)
4compound
The preparation of employing solid reaction process, the reaction equation of employing is 3Na
2o+3Y
2o
3+ 4B
2o
3=2Na
3y
3(BO
3)
4;
The proportioning of above-mentioned three kinds of reagent: Na
2o=5.780g (0.09mol); Y
2o
3=20.324g (0.09mol); B
2o
3=8.354g (0.12mol);
Its concrete preparation process is: by above-mentioned dosage, take respectively reagent, they are placed in mortar, are carefully ground, then pack in the crucible of Φ 50mm × 50mm, by its compacting, put into retort furnace, with the speed of 50 ℃/h, be warming up to 500 ℃ of pre-burnings, cooling after insulation 24h, taking out after cooling sample is reground, be placed in crucible and compacting, sintering 24h at 1100 ℃ in retort furnace, can take out midway and grind 1～2 time again; After cooling, crucible is taken out, in mortar, smash grinding to pieces and can obtain Powdered Na
3y
3(BO
3)
4compound, this Powdered Na
3y
3(BO
3)
4the XRD figure of compound is composed as shown in Figure 2.
Embodiment 2: prepare Powdered Na
3y
3(BO
3)
4compound
The preparation of employing solid reaction process;
The reaction equation adopting is: 3Na
2cO
3+ 3Y
2o
3+ 8H
3bO
3=2Na
3y
3(BO
3)
4+ 3CO
2↑+12H
2o ↑
The proportioning of above-mentioned three kinds of reagent: Na
2cO
3=9.539g (0.09mol); Y
2o
3=20.324g (0.09mol); H
3bO
3=14.839g (0.24mol);
Its concrete preparation process is: by above-mentioned dosage, take respectively reagent, they are placed in mortar, are carefully ground, then pack in the crucible of Φ 50mm × 50mm, by its compacting, put into retort furnace, with the speed of 30 ℃/h, be warming up to 500 ℃ of pre-burnings, insulation 48h, taking out after cooling sample is reground, be placed in crucible and compacting, sintering 48h at 800 ℃ in retort furnace, takes out and grinds 1～2 time midway again.After cooling, crucible is taken out, in mortar, smash grinding to pieces and can obtain Powdered Na
3y
3(BO
3)
4compound, this Powdered Na
3y
3(BO
3)
4the XRD figure of compound is composed as shown in Figure 2.
Embodiment 3: prepare Powdered Na
3y
3(BO
3)
4compound
The preparation of employing solid reaction process;
The reaction equation adopting is as follows:
12NaNO
3+6Y
2O
3+16H
3BO
3=4Na
3Y
3(BO
3)
4+12NO
2↑+24H
2O↑+3O
2↑
The proportioning of above-mentioned three kinds of reagent: NaNO
3=15.300g (0.18mol); Y
2o
3=40.648g (0.18mol); H
3bO
3=14.839g (0.24mol).
Its concrete preparation process is: by above-mentioned dosage, take respectively reagent, they are placed in mortar, are carefully ground, then pack in the crucible of Φ 50mm × 50mm, by its compacting, put into retort furnace, with the speed of 40 ℃/h, be warming up to 500 ℃ of pre-burnings, insulation 36h, taking out after cooling sample is reground, be placed in crucible and compacting, sintering 36h at 900 ℃ in retort furnace, takes out and grinds 1～2 time midway again.After cooling, crucible is taken out, in mortar, smash grinding to pieces and can obtain Powdered Na
3y
3(BO
3)
4compound, Powdered Na
3y
3(BO
3)
4the XRD figure of compound is composed as shown in Figure 2.
Embodiment 4: prepare Powdered Na
3y
3(BO
3)
4compound
The preparation of employing solid reaction process;
The reaction equation adopting is as follows:
3Na
2CO
3+3Y
2(CO
3)
3+8H
3BO
3=2Na
3Y
3(BO
3)
4+12H
2O↑+12CO
2↑
The proportioning of above-mentioned three kinds of reagent: Na
2cO
3=9.539g (0.09mol); Y
2(CO
3)
3=21.405g (0.09mol); H
3bO
3=14.839g (0.24mol);
Concrete preparation process is: by above-mentioned dosage, take respectively reagent, they are placed in mortar, are carefully ground, then mixture is packed in the crucible of Φ 50mm × 50mm, by its compacting, put into retort furnace, with the speed of 20 ℃/h, be warming up to 500 ℃ of pre-burnings, insulation 48h, taking out after cooling sample is reground, be placed in crucible and compacting, sintering 72h at 1000 ℃ in retort furnace, takes out and grinds 1～2 time midway again.After cooling, crucible is taken out, in mortar, smash grinding to pieces and can obtain powder Na
3y
3(BO
3)
4compound, the XRD figure of product is composed as shown in Figure 2.
Embodiment 5: adopt molten-salt growth method to prepare Na
3y
3(BO
3)
4non-linear optic crystal 2-1.5
Press fusing assistant Na
2cO
3: H
3bO
3: NaF mol ratio be 1:1:2 as flux, by solute and flux mol ratio, be 1:25 (referring to the ratio of the mole number of solute and the total mole number of flux), take respectively 82.142gNa
2cO
3, 33.872gY
2o
3, 57.196gH
3bO
3and 52.488gNaF (that is to say Na
3y
3(BO
3)
4: Na
2cO
3: H
3bO
3: NaF=1:6.25:6.25:12.5), after being ground in mortar, pack in the crucible of Φ 90mm × 80mm, crucible is placed in retort furnace, with the speed of 20 ℃/h, be warming up to 500 ℃, cooling after pre-burning 24h, cooling rear taking-up, then raw material is smashed to pieces and is ground, be fused in batches in the crucible of Φ 60mm × 60mm; Crucible after material is put into vertical crystal growing furnace, the fire door that is positioned at furnace roof portion with lagging material handle is sealed up, in furnace roof portion and corresponding position, crucible center, stay an aperture that can stretch into for seed rod, be warming up to 1100 ℃, constant temperature stirs after 48h, then be cooled to 1000 ± 2 ℃, platinum filament is fixed on to seed rod lower end, from furnace roof portion aperture, seed crystal is imported to crucible, make it to contact with liquation liquid level, with the speed cooling of 10 ℃/day, treat to separate out on platinum filament the Na of large-size, partially transparent
3y
3(BO
3)
4crystal, proposes liquid level by crystal, with the speed of 30 ℃/h, is cooled to room temperature, cuts gained crystal mass preferably partly as seed crystal; Again raw material is heated up and melted, constant temperature 24h, adopts trial seed crystal method accurately to record the temperature of saturation of system, then cools to above 10 ℃ of temperature of saturation, by Na
3y
3(BO
3)
4small-crystalline is fixed on seed rod, stretches into lentamente in the melt of crucible, and starts the wheelwork of seed rod upper end, and slewing rate is 20 revs/min, is cooled to temperature of saturation in 30min, after constant temperature 24h, with the speed cooling of 1 ℃/day, starts crystal growth; In rotation process, can regulate rate of temperature fall or slewing rate or their combination, control the speed of growth of crystal; After crystal growth finishes, promote seed rod, crystal is lifted to liquid level, then with the speed of 30 ℃/h, be cooled to room temperature, obtain transparent Na
3y
3(BO
3)
4non-linear optic crystal.
Embodiment 6: adopt molten-salt growth method to prepare Na
3y
3(BO
3)
4crystal
Press fusing assistant Na
2cO
3: H
3bO
3: NaF mol ratio is 1:1:1, and solute/flux mol ratio is 1:10 (referring to the ratio of the mole number of solute and the total mole number of flux), takes 76.312gNa
2cO
3, 50.810gY
2o
3, 67.709gH
3bO
3, 20.786gNaF (that is to say Na
3y
3(BO
3)
4: Na
2cO
3: H
3bO
3: NaF=1:3.3:3.3:3.3), after being ground in mortar, pack in the crucible of Φ 90mm × 80mm, crucible is placed in retort furnace, with the speed of 50 ℃/h, be warming up to 500 ℃, pre-burning 72h, cooling rear taking-up, then raw material is smashed to pieces and is ground, be fused in batches in the crucible of Φ 60mm × 60mm.Crucible after material is put into vertical crystal growing furnace, be warming up to 1150 ℃, constant temperature stirs after 24h, adopts trial seed crystal method accurately to record the temperature of saturation of system, is then cooled to above 20 ℃ of temperature of saturation, by Na
3y
3(BO
3)
4small-crystalline is fixed on seed rod, from furnace roof down to liquid level, cools to temperature of saturation in 30min, and after constant temperature 24h, with the speed cooling growth of 0.5 ℃/day, controlling seed rotation rate is 40 revs/min; After crystal growth finishes, crystal is lifted to liquid level, then with the speed of 40 ℃/h, be cooled to room temperature, obtain transparent Na
3y
3(BO
3)
4crystal.
Embodiment 7: adopt molten-salt growth method to prepare Na
3y
3(BO
3)
4crystal
Press fusing assistant Na
2cO
3: H
3bO
3: NaF mol ratio is 0:0:1, and solute/flux mol ratio is 1:30 (referring to the ratio of the mole number of solute and the total mole number of flux), takes 15.899gNa
2cO
3, 33.872gY
2o
3, 18.550gH
3bO
3, 125.970gNaF (that is to say Na
3y
3(BO
3)
4: Na
2cO
3: H
3bO
3: NaF=1:0:0:30), after being ground in mortar, pack in the crucible of Φ 90mm × 80mm, crucible is placed in retort furnace, with the speed of 30 ℃/h, be warming up to 500 ℃, pre-burning 36h, cooling rear taking-up, then raw material is smashed to pieces and is ground, be fused in batches in the crucible of Φ 60mm × 60mm.Crucible after material is put into vertical crystal growing furnace, be warming up to 1080 ℃, constant temperature stirs after 36h, adopts trial seed crystal method accurately to record the temperature of saturation of system, is then down to above 15 ℃ of temperature of saturation, by Na
3y
3(BO
3)
4small-crystalline is fixed on seed rod, from furnace roof down to liquid level, cools to temperature of saturation in 30min, and after constant temperature 24h, with the speed cooling of 1.5 ℃/day, slewing rate is 30 revs/min.After crystal growth finishes, crystal is lifted to liquid level, then with the speed of 20 ℃/h, be cooled to room temperature, obtain transparent Na
3y
3(BO
3)
4crystal.
Embodiment 8: adopt molten-salt growth method to prepare Na
3y
3(BO
3)
4crystal
Press fusing assistant Na
2cO
3: H
3bO
3: NaF mol ratio is 1.5:1.5:1, and solute/flux mol ratio is 1:20 (referring to the ratio of the mole number of solute and the total mole number of flux), takes 95.392gNa
2cO
3, 33.872gY
2o
3, 71.105gH
3bO
3, 20.994gNaF, after being ground in mortar, pack in the crucible of Φ 90mm × 80mm, crucible is placed in retort furnace, with the speed of 20 ℃/h, is warming up to 500 ℃, pre-burning 24h, cooling rear taking-up, then smashs raw material to be ground to pieces, is fused in batches in the crucible of Φ 60mm × 60mm.Crucible after material is put into vertical crystal growing furnace, be warming up to 1050 ℃, constant temperature stirs after 48h, adopts trial seed crystal method accurately to record the temperature of saturation of system, is then down to above 20 ℃ of temperature of saturation, by Na
3y
3(BO
3)
4small-crystalline is fixed on seed rod, from furnace roof down to liquid level, cools to temperature of saturation in 30min, and after constant temperature 24h, with the speed cooling of 1 ℃/day, slewing rate is 30 revs/min.After crystal growth finishes, crystal is lifted to liquid level, then with the speed of 20 ℃/h, be cooled to room temperature, obtain transparent Na
3y
3(BO
3)
4crystal.
Embodiment 9: adopt molten-salt growth method to prepare Na
3y
3(BO
3)
4crystal
The Na preparing with embodiment 2
3y
3(BO
3)
4powder is raw material, Na
2cO
3-H
3bO
3-NaF is as fusing assistant, according to mol ratio Na
3y
3(BO
3)
4: Na
2cO
3: H
3bO
3: NaF=1:7:6:9 (that is to say solute: flux mol ratio is 1:22, Na in flux
2cO
3: H
3bO
3: NaF mol ratio is 1:0.9:1.3), take respectively 57.094gNa
3y
3(BO
3)
4, 74.193gNa
2cO
3, 37.101
gh
3bO
3, 37.792gNaF, after being ground in mortar, be fused in the crucible of Φ 60mm × 60mm in batches.The crucible that fills raw material is put into vertical crystal growing furnace, be warming up to 1100 ℃, constant temperature stirs after 48h, adopts trial seed crystal method accurately to record the temperature of saturation of system, then cools to above 20 ℃ of temperature of saturation, then by Na
3y
3(BO
3)
4small-crystalline is fixed on seed rod, from furnace roof down to liquid level, is cooled to temperature of saturation in 30min, and after constant temperature 24h, with the speed cooling of 0.2 ℃/day, slewing rate is 30 revs/min.After crystal growth finishes, crystal is lifted to liquid level, then with the speed of 20 ℃/h, be cooled to room temperature, obtain transparent Na
3y
3(BO
3)
4crystal.
Embodiment 10: adopt molten-salt growth method to prepare Na
3y
3(BO
3)
4crystal
The Na preparing with embodiment 2
3y
3(BO
3)
4powder is raw material, Na
2cO
3-H
3bO
3as fusing assistant, according to mol ratio Na
3y
3(BO
3)
4: Na
2cO
3: H
3bO
3=1:7:7 (that is to say solute: flux mol ratio is 1:14, Na in flux
2cO
3: H
3bO
3mol ratio is 1:1), take respectively 57.094gNa
3y
3(BO
3)
4, 74.193gNa
2cO
3, 43.284gH
3bO
3, after being ground in mortar, be fused in the crucible of Φ 60mm × 60mm in batches.The crucible that fills raw material is put into vertical crystal growing furnace, be warming up to 1150 ℃, constant temperature stirs after 48h, adopts trial seed crystal method accurately to record the temperature of saturation of system, then cools to above 30 ℃ of temperature of saturation, by Na
3y
3(BO
3)
4small-crystalline is fixed on seed rod, from furnace roof down to liquid level, cools to temperature of saturation in 30min, and after constant temperature 24h, with the speed cooling growth of 2 ℃/day, slewing rate is 20 revs/min.After crystal growth finishes, crystal is lifted to liquid level, then with the speed of 50 ℃/h, be cooled to room temperature, obtain transparent Na
3y
3(BO
3)
4crystal.
Embodiment 11: adopt Na
3y
3(BO
3)
4non-linear optic crystal is made device for non-linear optical
By embodiment 5,6,7,8 or 9 gained Na
3y
3(BO
3)
4non-linear optic crystal is made sectional dimension 4 × 4mm, the quartz crystal device of optical direction length 6mm;
Press shown in accompanying drawing 1, by quartz crystal device device position of 3 in Fig. 1, at room temperature, and with adjusting QNd:YAG laser apparatus to make light source, the infrared light that incident wavelength is 1064nm, the green laser that output wavelength is 532nm, laser intensity is about 2～4 times of KDP (KH
2pO
4);
Fig. 1 adopts Na to the present invention
3y
3(BO
3)
4the device for non-linear optical that single crystal is made elaborates; The light beam 2 being sent by laser apparatus 1 is injected Na
3y
3(BO
3)
4 non-linear optic crystal 3, the outgoing beam 4 producing passes through filter plate 5, thereby obtains needed laser beam; This nonlinear optics laser apparatus can be 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, and concerning using Nd:YAG laser apparatus to do the frequency doubling device of light source, incoming beam is that wavelength is the infrared light of 1064nm, passes through Na
3y
3(BO
3)
4crystal produces the green frequency doubled light that wavelength is 532nm, and it is the infrared light of 1064nm and the green glow of 532nm that outgoing beam 4 contains wavelength, and the effect of spectral filter 5 is to filter infrared light, only allows green glow to pass through.
Claims (7)
1. a yttrium borate sodium compound, its chemical formula is Na
3y
3(BO
3)
4.
2. the preparation method of yttrium borate sodium compound described in a claim 1, it adopts chemical synthesis preparation: will be containing Na compound, contain after Y compound and boride alloy mix and pack crucible compacting into, be placed in retort furnace and be warmed up to 500 ℃ of pre-burning 24～48h with the temperature rise rate of 20 ℃/h～50 ℃/h, again grind evenly after cooling, again pack crucible and compacting into and be placed in retort furnace in 800～1100 ℃ of sintering 24～72h;
Described is 3:3:4 containing Na compound, containing the mol ratio of contained Na, Y and B in Y compound and the mixed uniformly mixture of boride alloy;
Described is sodium oxide, sodium carbonate, SODIUMNITRATE, sodium oxalate or sodium hydroxide containing Na compound;
Described is yttrium oxide, yttrium carbonate, Yttrium trinitrate, yttrium oxalate or yttrium hydroxide containing Y compound;
Described boride alloy is H
3bO
3or B
2o
3.
3. a yttrium borate sodium non-linear optic crystal, is characterized in that, its chemical formula is Na
3y
3(BO
3)
4; This crystal does not have symmetry centre, belongs to hexagonal system, and spacer is P6
3mc (No.186), unit cell parameters is: a=10.1136 (14)
b=10.1136 (14)
c=6.7485 (13)
α=β=90 °, γ=120 °, Z=2, V=597.79 (2)
density is 3.172g/cm
3.
4. the growth method of yttrium borate sodium non-linear optic crystal described in a claim 3, it adopts fusing assistant molten-salt growth, its growth step is as follows: using yttrium borate sodium compound as solute, fusing assistant is as flux, the abundant ground and mixed of ratio that by solute and flux is in molar ratio 1～10:1～30 in agate mortar is even, is packed into crucible and compacting and puts into retort furnace and carry out pre-treatment; Again pretreated mixture is melted in growth crucible in batches, growth crucible is placed in to crystal growing furnace and is heated to the liquation of mixture melt; And constant temperature stirs 24～72h, use and attempt seed crystal and record the temperature of saturation of system, more than temperature of saturation 10～30 ℃, the seed crystal being contained on seed rod is stretched in molten surface or liquation, and starting the rotating mechanism on seed rod, the speed of rotation of seed rod is 0～40 rev/min; In 30min, be cooled to temperature of saturation, after constant temperature 24h, with the speed cooling growing crystal of 0.2～2 ℃/day; The sense of rotation of seed rod is the bidirectional rotation that clockwise direction, counter clockwise direction or clockwise direction and counter clockwise direction hocket; After crystal grows into required yardstick, promote seed rod, make seed crystal depart from liquation liquid level; Crystal is stayed in growth furnace and is annealed, and with the speed that is not more than 50 ℃/h, is cooled to room temperature, obtains yttrium borate sodium non-linear optic crystal, and its chemical formula is Na
3y
3(BO
3)
4;
Described fusing assistant is Na
2cO
3-H
3bO
3-NaF system fusing assistant or Na
2cO
3-H
3bO
3system fusing assistant;
Described Na
2cO
3-H
3bO
3na in-NaF system fusing assistant
2cO
3: H
3bO
3: NaF mol ratio is 0～1.5:0～1.5:1～2; Described Na
2cO
3-H
3bO
3na in system fusing assistant
2cO
3: H
3bO
3mol ratio is 1:1.
5. by the growth method of yttrium borate sodium non-linear optic crystal claimed in claim 4, it is characterized in that, described pre-treatment refers to the solute and the flux mixture that fully grind is packed in crucible and be placed in retort furnace, with the temperature rise rate of 20～50 ℃/h, is warmed up to 500 ℃ of sintering 24～48h.
6. by the growth method of yttrium borate sodium non-linear optic crystal claimed in claim 4, it is characterized in that, described yttrium borate sodium compound solute is by containing Na compound, being the mixture replacing that 3:3:4 ratio forms containing Y compound and boride alloy in Na:Y:B mol ratio wherein;
Described is sodium oxide, sodium carbonate, SODIUMNITRATE, sodium oxalate or sodium hydroxide containing Na compound;
Described is yttrium oxide, yttrium carbonate, Yttrium trinitrate, yttrium oxalate or yttrium hydroxide containing Y compound;
Described boride alloy is H
3bO
3or B
2o
3.
7. the purposes of a yttrium borate sodium non-linear optic crystal claimed in claim 4, it is characterized in that, yttrium borate sodium non-linear optic crystal is for the preparation of device for non-linear optical, and described device for non-linear optical comprises at least a branch of incidence electromagnetic radiation is produced to the device that at least a branch of frequency is different from the output radiation of incidence electromagnetic radiation after by least one block of yttrium borate sodium non-linear optic crystal.
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| CN106319624A (en) * | 2016-09-20 | 2017-01-11 | 河南理工大学 | Photoluminescent crystalline material sodium samarium borate and preparation method and application thereof |
| CN106480500A (en) * | 2016-10-08 | 2017-03-08 | 河南理工大学 | A kind of luminescence generated by light crystalline material boric acid praseodymium potassium and its preparation method and application |
| CN109763169A (en) * | 2019-03-06 | 2019-05-17 | 中国科学院新疆理化技术研究所 | Potassium borate lutetium nonlinear optical crystal and its preparation method and application |
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| CN115341262A (en) * | 2022-07-29 | 2022-11-15 | 中国科学院理化技术研究所 | Gadolinium-based borate crystal and preparation method and application thereof |
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| CN106319624A (en) * | 2016-09-20 | 2017-01-11 | 河南理工大学 | Photoluminescent crystalline material sodium samarium borate and preparation method and application thereof |
| CN106480500A (en) * | 2016-10-08 | 2017-03-08 | 河南理工大学 | A kind of luminescence generated by light crystalline material boric acid praseodymium potassium and its preparation method and application |
| CN106745023B (en) * | 2016-12-02 | 2021-07-02 | 河南理工大学 | Compound hafnium sodium borate luminescent crystal material, preparation method and application |
| CN109763169A (en) * | 2019-03-06 | 2019-05-17 | 中国科学院新疆理化技术研究所 | Potassium borate lutetium nonlinear optical crystal and its preparation method and application |
| CN115341262A (en) * | 2022-07-29 | 2022-11-15 | 中国科学院理化技术研究所 | Gadolinium-based borate crystal and preparation method and application thereof |
| CN115341262B (en) * | 2022-07-29 | 2023-08-01 | 中国科学院理化技术研究所 | Gadolinium-based borate crystal and preparation method and application thereof |
| WO2024027105A1 (en) * | 2022-08-05 | 2024-02-08 | 广东省科学院资源利用与稀土开发研究所 | Lithium sodium yttrium borate and cerium-doped compound and crystal thereof, and preparation methods therefor and use thereof |
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