CN102828246B - Strontium sodium fluoroboroberyllate nonlinear optical crystal and growth method and application thereof - Google Patents
Strontium sodium fluoroboroberyllate nonlinear optical crystal and growth method and application thereof Download PDFInfo
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- CN102828246B CN102828246B CN201110159659.8A CN201110159659A CN102828246B CN 102828246 B CN102828246 B CN 102828246B CN 201110159659 A CN201110159659 A CN 201110159659A CN 102828246 B CN102828246 B CN 102828246B
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- 239000013078 crystal Substances 0.000 title claims abstract description 133
- 230000003287 optical effect Effects 0.000 title claims abstract description 37
- 238000000034 method Methods 0.000 title claims abstract description 22
- KWVFUTDPKIKVQW-UHFFFAOYSA-N [Sr].[Na] Chemical compound [Sr].[Na] KWVFUTDPKIKVQW-UHFFFAOYSA-N 0.000 title abstract 3
- 238000001816 cooling Methods 0.000 claims abstract description 13
- 239000007788 liquid Substances 0.000 claims abstract description 10
- 238000006243 chemical reaction Methods 0.000 claims abstract description 5
- IIUWASLPDJGIAX-UHFFFAOYSA-N [F].[Sr] Chemical compound [F].[Sr] IIUWASLPDJGIAX-UHFFFAOYSA-N 0.000 claims description 40
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 34
- 229910052708 sodium Inorganic materials 0.000 claims description 34
- 239000011734 sodium Substances 0.000 claims description 34
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 22
- 239000000203 mixture Substances 0.000 claims description 12
- 229910052697 platinum Inorganic materials 0.000 claims description 11
- 230000010355 oscillation Effects 0.000 claims description 8
- 150000003388 sodium compounds Chemical class 0.000 claims description 8
- 239000000835 fiber Substances 0.000 claims description 5
- 230000002457 bidirectional effect Effects 0.000 claims description 4
- 230000002441 reversible effect Effects 0.000 claims description 4
- 238000005245 sintering Methods 0.000 claims description 3
- 238000010532 solid phase synthesis reaction Methods 0.000 claims description 3
- 125000006850 spacer group Chemical group 0.000 claims description 3
- 238000002360 preparation method Methods 0.000 claims description 2
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 claims 2
- 229910052731 fluorine Inorganic materials 0.000 claims 2
- 239000011737 fluorine Substances 0.000 claims 2
- 229910052712 strontium Inorganic materials 0.000 claims 2
- CIOAGBVUUVVLOB-UHFFFAOYSA-N strontium atom Chemical compound [Sr] CIOAGBVUUVVLOB-UHFFFAOYSA-N 0.000 claims 2
- 238000010438 heat treatment Methods 0.000 abstract description 15
- 239000003795 chemical substances by application Substances 0.000 abstract description 2
- 238000004519 manufacturing process Methods 0.000 abstract description 2
- JZKFIPKXQBZXMW-UHFFFAOYSA-L beryllium difluoride Chemical compound F[Be]F JZKFIPKXQBZXMW-UHFFFAOYSA-L 0.000 abstract 1
- 230000001427 coherent effect Effects 0.000 abstract 1
- 150000003839 salts Chemical class 0.000 abstract 1
- 239000000126 substance Substances 0.000 abstract 1
- 239000002994 raw material Substances 0.000 description 14
- 229910052790 beryllium Inorganic materials 0.000 description 12
- ATBAMAFKBVZNFJ-UHFFFAOYSA-N beryllium atom Chemical compound [Be] ATBAMAFKBVZNFJ-UHFFFAOYSA-N 0.000 description 11
- 150000001875 compounds Chemical class 0.000 description 8
- 239000000463 material Substances 0.000 description 8
- 238000010792 warming Methods 0.000 description 8
- 230000000694 effects Effects 0.000 description 7
- 238000002844 melting Methods 0.000 description 7
- 230000008018 melting Effects 0.000 description 7
- 238000010583 slow cooling Methods 0.000 description 7
- 238000010521 absorption reaction Methods 0.000 description 4
- 239000012071 phase Substances 0.000 description 4
- 230000010287 polarization Effects 0.000 description 4
- 239000000843 powder Substances 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 3
- 125000001153 fluoro group Chemical group F* 0.000 description 2
- 238000002211 ultraviolet spectrum Methods 0.000 description 2
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical group [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 230000003321 amplification Effects 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- QBLDFAIABQKINO-UHFFFAOYSA-N barium borate Chemical compound [Ba+2].[O-]B=O.[O-]B=O QBLDFAIABQKINO-UHFFFAOYSA-N 0.000 description 1
- 150000001572 beryllium Chemical class 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 238000002109 crystal growth method Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- PSHMSSXLYVAENJ-UHFFFAOYSA-N dilithium;[oxido(oxoboranyloxy)boranyl]oxy-oxoboranyloxyborinate Chemical compound [Li+].[Li+].O=BOB([O-])OB([O-])OB=O PSHMSSXLYVAENJ-UHFFFAOYSA-N 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000008204 material by function Substances 0.000 description 1
- 239000004570 mortar (masonry) Substances 0.000 description 1
- 238000003199 nucleic acid amplification method Methods 0.000 description 1
- 230000005693 optoelectronics Effects 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- WYOHGPUPVHHUGO-UHFFFAOYSA-K potassium;oxygen(2-);titanium(4+);phosphate Chemical compound [O-2].[K+].[Ti+4].[O-]P([O-])([O-])=O WYOHGPUPVHHUGO-UHFFFAOYSA-K 0.000 description 1
- 238000000634 powder X-ray diffraction Methods 0.000 description 1
- 229910001419 rubidium ion Inorganic materials 0.000 description 1
- 238000003746 solid phase reaction Methods 0.000 description 1
- 238000010671 solid-state reaction Methods 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
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- Crystals, And After-Treatments Of Crystals (AREA)
Abstract
NaSr3Be3B3O9F4The nonlinear optical crystal is prepared by adopting a molten salt growth method: uniformly mixing strontium sodium fluoroboroberyllate and a fluxing agent in proportion, heating to 850 ℃, keeping the temperature constant, and cooling to 2-10 ℃ above the saturation temperature to obtain a high-temperature solution; putting seed crystals into the high-temperature solution, rotating a seed crystal rod, cooling to a saturation temperature, slowly cooling, lifting the crystals out of the liquid level, and cooling to room temperature to obtain the strontium sodium fluoroberyllate nonlinear optical crystals; the crystal has a nonlinear optical effect, has wide light-transmitting wave band, ultraviolet cut-off edge reaching 170nm, is not deliquesced, has good chemical stability, is suitable for the frequency conversion requirement of ultraviolet wave band laser, can be used for manufacturing nonlinear optical devices, can realize harmonic light output devices of 2 frequency multiplication, 3 frequency multiplication, 4 frequency multiplication, 5 frequency multiplication or 6 frequency multiplication of Nd: YAG laser, and can also be used for harmonic light output devices of other laser wavelengths, thereby generating coherent light output with the wavelength equal to or shorter than 266 nm.
Description
Technical field
The present invention relates to a kind of optoelectronic functional materials and growth method and purposes, particularly relate to a kind of nonlinear optical material and its production and use, specifically, relate to a kind of beryllium fluoroborate (NaSr
3be
3b
3o
9f
4) non-linear optic crystal and growth method and purposes.Described fluorine strontium boroberyllate sodium (NaSr
3be
3b
3o
9f
4) abbreviation NSBBF.
Background technology
The non-linear optical effect of crystal refers to a kind of like this effect: when a branch of laser with certain polarization direction and certain incident direction passes through a non-linear optic crystal (as NSBBF of the present invention), the frequency of this laser beam will change.Fig. 1 and Fig. 2 are the canonical schema of this effect.
The crystal with non-linear optical effect is called non-linear optic crystal.Here non-linear optical effect refers to the effects such as frequency multiplication and frequency, difference frequency, optical parametric oscillation and optical parameter amplification.Only have the crystal without symmetry centre just may have non-linear optical effect.Utilize the non-linear optical effect of crystal, can make second harmonic generator, upper and lower frequency converter, the 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, for example, pass through non-linear optic crystal, can make a branch of infrared laser beam (for example 1064nm) make it transform to visible ray, UV-light even deep ultraviolet spectrum district (wavelength is shorter than 200nm), thereby have huge application prospect at laser technology field.That this wave band is the most frequently used at present is three kinds of inorganic nonlinear optical crystals, i.e. low-temperature phase barium metaborate (β-BaB
2o
4, be called for short BBO), three lithium tetraborate (LiB
3o
5, be called for short LBO) and potassium titanium oxide phosphate (KTiOPO
4, be called for short KTP).But effective frequency multiplication output wavelength of these three kinds of crystal is all subject to certain limitation in UV spectrum district.For BBO, due to (1) (B
3o
6) group has the large π orbital characteristics of gripping altogether, makes the band gap red shift of group, this causes the ABSORPTION EDGE of bbo crystal at 189nm; (2) be subject to the restriction of ultraviolet absorption edge, this crystal cannot be produced be shorter than the humorous glistening light of waves of 193nm; (3) plane (B
3o
6) group causes the degree of birefringence Δ n ≈ 0.12 of bbo crystal, large degree of birefringence makes bbo crystal at the acceptance angle Δ θ=0.45mrad*cm at quadruple place, and this device for practical application is too little.And for LBO, because degree of birefringence is too little, can not in shorter wave band, realize phase matched and produce the output of effective frequency doubled light.For ktp crystal, its cut-off wave band is 350nm, therefore can not produce the humorous glistening light of waves of ultraviolet.[BBO (β-BaB
2o
4), referring to < < Chinese science > > B28,235,1985; LBO (LiB
3o
5) crystal, referring to < < Chinese invention patent > > 88102084; KTP (KTiOPO
4), referring to Handbook of Nonlinear Optical crystals]
At present, can produce deep ultraviolet direct frequency doubling output non-linear optic crystal only have KBe
2bO
3f
2(being called for short KBBF) and RbBe
2bO
3f
2(being called for short RBBF).KBBF and RBBF crystal are by plane trigonometry type (BO
3) group and tetrahedral (BeO
3f) group forms, (BO
3) three Sauerstoffatoms of group are connected with Be atom, form two-dimentional infinite network, K
+and Rb
+ion, between multi-layered network, relies on electrostatic force to interconnect between layers.The non-linear optical effect of crystal is mainly by (BO
3) group generation, (BO
3) group presents plane arrangement in lattice, be parallel to each other and perpendicular to the axle of crystal, make crystal there is outstanding nonlinear optical property.The ABSORPTION EDGE of this crystalloid in ultraviolet region is 150nm left and right, and degree of birefringence is 0.07 left and right, and KBBF direct frequency doubling may be output to 161nm (RBBF is 171nm).Utilize prism-coupled technology, KBBF crystal has been realized the humorous glistening light of waves output of quadruple of Ti:sapphire laser and the six humorous glistening light of waves outputs of frequency multiplication [referring to Appl.phys.B 2009,97,9-25] of Nd base laser; RBBF crystal is also [referring to J.Opt.Soc.Am.B2009,26,1519-1525] like this.
Summary of the invention
The object of the present invention is to provide a kind of fluorine strontium boroberyllate sodium (NaSr
3be
3b
3o
9f
4, be called for short NSBBF) and non-linear optic crystal, this crystal is suitable for the needs of ultraviolet band laser frequency conversion, can be used for making device for non-linear optical, can realize 2 frequencys multiplication of Nd:YAG laser, 3 frequencys multiplication, 4 frequencys multiplication, 5 frequencys multiplication, are even shorter than the frequency multiplication output of 200nm.
Another object of the present invention is to provide fluorine strontium boroberyllate sodium non-linear optic crystal growth method, this growing method is convenient and swift;
A further object of the present invention is to provide the purposes of fluorine strontium boroberyllate sodium non-linear optic crystal, this fluorine strontium boroberyllate sodium crystal can be realized 2 frequency multiplication 3 frequencys multiplication, 4 frequencys multiplication, 5 frequencys multiplication of Nd:YAG laser, even also has the ability to produce the output that wavelength is shorter than the humorous glistening light of waves of 200nm; This fluorine strontium boroberyllate sodium non-linear optic crystal will be at various non-linear optical fields (as electro-optical device, pyroelectric electric device, harmonic generators, optical parametric oscillation and photoparametric amplifier part, fiber waveguide device etc.) in, obtain widespread use, and by the nonlinear optics application of developing vacuum ultraviolet.
Technical scheme of the present invention is as follows:
Fluorine strontium boroberyllate sodium non-linear optic crystal provided by the invention, its molecular formula is NaSr
3be
3b
3o
9f
4, belonging to trigonal system, spacer is R3m, fusing point is about 850 ℃, deliquescence not in air, molecular weight is 565.31, cell parameter is
α=β=90 °, γ=120 °,
z=3;
The molten-salt growth method of fluorine strontium boroberyllate sodium non-linear optic crystal provided by the invention, its concrete steps are as follows:
(1) within putting into the platinum crucible of crystal growing furnace after fluorine strontium boroberyllate sodium compound and fusing assistant being mixed in molar ratio evenly, with the temperature rise rates of 10～30 ℃/h, be heated to 850 ℃, constant temperature 10～40 hours, be cooled to again on temperature of saturation 2～10 ℃, obtain the pyrosol that contains fluorine strontium boroberyllate sodium compound and fusing assistant;
Described fusing assistant is B
2o
3, NaF and SrF
2the mixture forming;
The mol ratio of described fluorine strontium boroberyllate sodium and fusing assistant is NaSr
3be
3b
3o
9f
4: B
2o
3: NaF: SrF
2=1: (0.5～1): (3.5～5): (0.4～1);
(2) seed rod that seed crystal is housed is put into the pyrosol that contains fluorine strontium boroberyllate sodium compound and fusing assistant that above-mentioned steps (1) obtains from crystal growing furnace top, simultaneously with the speed rotary seed crystal rod of 10-100 rev/min, be cooled to temperature of saturation, then with the speed of 0.5～1.5 ℃/day, lower the temperature, after cooling finishes, gained crystal is lifted to liquid level, and be down to room temperature with the speed of 5～15 ℃/h, obtain fluorine strontium boroberyllate sodium non-linear optic crystal, its molecular formula is NaSr
3be
3b
3o
9f
4.
In described step (2), the sense of rotation of seed rod is single direction rotation or bidirectional reversible rotation.Each one direction rotational time in described bidirectional reversible rotation is 1～10 minute; The timed interval of adjacent two one directions rotation is 0.5～1 minute.
The purposes of beryllium fluoroborate non-linear optic crystal of the present invention, but its its harmonic wave light output device of realizing 2 frequencys multiplication, 3 frequencys multiplication, 4 frequencys multiplication, 5 frequencys multiplication or 6 frequencys multiplication and be shorter than the humorous glistening light of waves output of 200nm for the preparation of the laser beam that to wavelength X is 1.064 μ m.Described harmonic wave light output device is for producing the harmonic wave light output device lower than 200nm.Described harmonic wave light output device is harmonic generator, optical parametric oscillation and photoparametric amplifier part or the fiber waveguide device for ultraviolet region.Described harmonic generator is optical parametric oscillation and the photoparametric amplifier part from infrared to ultraviolet region.
Described NaSr
3be
3b
3o
9f
4compound can adopt at high temperature sintering and obtain (seeing embodiment 1) of solid phase synthesis process, and its reaction equation is:
3SrCO
3+6BeO+6H
3BO
3+2NaF+3SrF
2＝2NaSr
3Be
3B
3O
9F
4+3CO
2↑+9H
2O↑
Or 3SrCO
3+ 6BeO+3B
2o
3+ 2NaF+3SrF
2=2NaSr
3be
3b
3o
9f
4+ 3CO
2↑.
The NaSr of solid phase synthesis
3be
3b
3o
9f
4(NSBBF) polycrystal powder, through powder SHG effect test, confirms that this compound has powder SHG effect, and effect is about 5 times of KDP.
NaSr
3be
3b
3o
9f
4the molten-salt growth of non-linear optic crystal, with NaF, SrF
2and B
2o
3mixture be fusing assistant; With platinum crucible make container, resistance wire is made heating unit, is selected A1-708P type automatic temperature control instrument able to programme;
The fluorine strontium boroberyllate sodium non-linear optic crystal of growing is tested and is confirmed through single crystal structure:
NaSr
3be
3b
3o
9f
4non-linear optic crystal belongs to trigonal system, and spacer is R3m, and fusing point is 850 ℃, deliquescence not in air, and molecular weight is 565.31, cell parameter is
α=β=90 °, γ=120 °,
z=3; Its concrete structure is provided by Fig. 3; NaSr
3be
3b
3o
9f
4structure mainly contains following characteristics: a beryllium atom and three oxygen and a fluorine atom form a BeO
3f tetrahedron, three BeO
3f tetrahedron and three BO
3plane triangle is alternately connected in the position of F atom, has formed by 12 Sauerstoffatoms and three beryllium atoms or and three large rings that comprise three six-rings that boron atom forms.These large rings are connected by Be-O-B covalent linkage each other, form three-dimensional structure; This structure makes the BO in NSBBF
3group approaches and is parallel to each other and arranges in the same way this BO
3the arrangement architecture in the same way of group is conducive to produce large macroscopical Clock Multiplier Factor, and powder SHG effect is about 5 times of KDP, simultaneously BO
3dangling bonds have been eliminated in Sauerstoffatom in group and the combination of beryllium atom, and the ultraviolet absorption edge of NSBBF is passed to 170nm left and right. and through measuring, the ultraviolet cut-on wavelength of NSBBF is λ ≈ 170nm; In addition, the connected structure of covalent linkage has been eliminated laminate structure and is made crystal more easily be grown to serve as bulk.
NaSr
3be
3b
3o
9f
4non-linear optic crystal can be realized two frequencys multiplication of Nd:YAG laser (λ=1.064 μ m), from theoretical and test result, can predict the humorous glistening light of waves output that NSBBF can show 3 frequencys multiplication, 4 frequencys multiplication, 5 frequencys multiplication of Nd:YAG laser (wavelength X=1.064 μ m) and be shorter than 200nm.So can predict, NSBBF crystal will obtain widespread use in various non-linear optical fields (harmonic generator, optical parametric oscillation and amplifying device and fiber waveguide device), and by the nonlinear optics application of developing vacuum ultraviolet.In addition, NSBBF crystal deliquescence not in air, fusing point is about 850 ℃.
Fluorine strontium boroberyllate sodium non-linear optic crystal of the present invention and growth method and purposes, its advantage is:
Growing method used is convenient and swift, and resulting crystal can be realized 2 frequency multiplication 3 frequencys multiplication, 4 frequencys multiplication, 5 frequencys multiplication of Nd:YAG laser, even also has the ability to produce the output that wavelength is shorter than the humorous glistening light of waves of 200nm.So, can predict this beryllium fluoroborate non-linear optic crystal will be at various non-linear optical fields (as electro-optical device, pyroelectric electric device, harmonic generators, optical parametric oscillation and photoparametric amplifier part, fiber waveguide device etc.) in, obtain widespread use, and by the nonlinear optics application of developing vacuum ultraviolet.
Accompanying drawing explanation
Fig. 1 is the canonical schema of fluorine strontium boroberyllate sodium non-linear optic crystal of the present invention while applying as frequency-doubling crystal, wherein: 1-laser apparatus, 2 and 3-reflective mirror, 4-half-wave plate, 5 and 6-set of lenses, 7-non-linear optic crystal NSBBF, 8-dispersing prism, ω and 2 ω are respectively fundamental wave and frequency doubled light.
Fig. 2 be fluorine strontium boroberyllate sodium non-linear optic crystal of the present invention as the canonical schema of other device for non-linear optical, wherein: 1-laser apparatus, 2 and 3-reflective mirror, 4-half-wave plate, 5 and 6-set of lenses, 7-non-linear optic crystal NSBBF, 8-dispersing prism, ω
1, ω
2-fundamental wave, ω
1+ ω
2be and frequency light, ω
1-ω
2it is difference frequency light.
Fig. 3 is NaSr
3be
3b
3o
9f
4the structural representation of non-linear optic crystal.
Embodiment
Embodiment 1
Synthetic NaSr
3be
3b
3o
9f
4the charging capacity of agents useful for same:
Concrete operation step is as follows:
By above-mentioned quality, in operation box, accurately weigh, put into agate mortar, mix and carefully grind, then pack into
cover in platinum crucible, by its compacting, (retort furnace is placed on ventilating kitchen to put into retort furnace, the exhaust of ventilating kitchen passes into water tank, discharge after filtering) in, slowly be warming up to 730 ℃ of sintering 48 hours, starting temperature rise rate must be slow, prevents from causing because of decomposition the variation of proportioning, and solid state reaction is fully carried out, be down to after room temperature, after taking-up is ground in operation box, then be placed in crucible and compacting, put into retort furnace, 730 ℃ of calcinations to the constant weight of take is reaction end, with powder x-ray diffraction, confirms that its product is NaSr
3be
3b
3o
9f
4compound pure phase.
Embodiment 2-8 is respectively the embodiment of fluorine strontium boroberyllate sodium (NSBBF) non-linear optic crystal growth:
Embodiment 2
The growth of NSBBF crystal, adopts molten-salt growth method, and crystal growing apparatus is Resistant heating stove, and temperature controlling instruments is A1-708P type automatic temperature control instrument able to programme; Concrete operations are: select the raw material of NSBBF (the resulting product of embodiment 1) or synthetic corresponding NSBBF compound, then add fusing assistant (B
2o
3, NaF and SrF
2the mixture forming) in following ratio, prepare 1mole NSBBF or with raw material (the 1.5mole SrCO that synthesizes 1mole NSBBF
3, 3mole BeO, 3mole H
3bO
3, 1mole NaF, 1.3mole SrF
2), then add solubility promoter (1mole B
2o
3, 5mole NaF and 1mole SrF
2the mixture forming), put into platinum crucible, then put into Resistant heating stove, with the temperature rise rates of 10 ℃/h, be warming up to 850 ℃, constant temperature is treated the abundant melting of material for 40 hours, is cooled to above 2 ℃ of temperature of saturation, obtains the pyrosol that contains fluorine strontium boroberyllate sodium compound and fusing assistant; The seed crystal being contained on seed rod is put into the pyrosol that contains fluorine strontium boroberyllate sodium compound and fusing assistant, with the speed rotary seed crystal rod of 10 revs/min, clockwise direction rotational time is 1 minute, pauses 0.5 minute simultaneously, then counterclockwise rotate 1 minute, with this reciprocation cycle; Be cooled to temperature of saturation (750 ℃), then, with the speed slow cooling of 0.5 ℃/day, after cooling finishes, can obtain required crystal, crystal is lifted to liquid level, speed with 5 ℃/h is down to room temperature, can obtain fluorine strontium boroberyllate sodium non-linear optic crystal.
Embodiment 3
The growth of NSBBF crystal, adopts molten-salt growth method, and crystal growing apparatus is Resistant heating stove, and temperature controlling instruments is A1-708P type automatic temperature control instrument able to programme; Concrete operations are: select the raw material of NSBBF (the resulting product of embodiment 1) or synthetic corresponding NSBBF compound, then add fusing assistant (B
2o
3, NaF and SrF
2the mixture forming), in following ratio, prepare: 1mole NSBBF or with raw material (the 1.5mole SrCO that synthesizes 1mole NSBBF
3, 3mole BeO, 3mole H
3bO
3, 1mole NaF and 1.3mole SrF
2), then add solubility promoter (0.5moleB
2o
3, 3.5mole NaF and 0.4mole SrF
2); Put into platinum crucible, then put into homemade electric Resistant heating stove, with the temperature rise rates of 30 ℃/h, be warming up to 850 ℃, constant temperature is treated the abundant melting of material for 10 hours, is cooled to above 10 ℃ of temperature of saturation, being contained in pyrosol while that seed crystal on seed rod puts into beryllium fluoroborate and fusing assistant speed rotary seed crystal rod with 100 revs/min, clockwise direction rotational time is 10 minutes, pause 1 minute, then counterclockwise rotate 10 minutes, with this reciprocation cycle; Be cooled to temperature of saturation (810 ℃), then, with the speed slow cooling of 1.5 ℃/day, after cooling finishes, can obtain required crystal, crystal is lifted to liquid level, speed with 15 ℃/h is down to room temperature, can obtain fluorine strontium boroberyllate sodium non-linear optic crystal.
Embodiment 4
The growth of NSBBF crystal, adopts molten-salt growth method, and crystal growing apparatus is homemade Resistant heating stove, and temperature controlling instruments is A1-708P type automatic temperature control instrument able to programme.Concrete operations are: select the raw material of NSBBF (the resulting product of embodiment 1) or synthetic corresponding NSBBF compound, then add fusing assistant (B
2o
3, NaF and SrF
2the mixture forming), in following ratio, prepare: 1mole NSBBF or with raw material (the 1.5mole SrCO that synthesizes 1mole NSBBF
3, 3mole BeO, 3mole H
3bO
3, 1mole NaF and 1.3mole SrF
2), then add solubility promoter (0.9moleB
2o
3, 4.5mole NaF and 1moleSrF
2); Put into platinum crucible, then put into Resistant heating stove, with the temperature rise rates of 12 ℃/h, be warming up to 850 ℃, constant temperature is treated the abundant melting of material for 20 hours, be cooled to above 5 ℃ of temperature of saturation, being contained in pyrosol while that seed crystal on seed rod puts into beryllium fluoroborate and fusing assistant clockwise single direction rotation seed rod of speed with 30 revs/min; Be cooled to temperature of saturation (765 ℃), then, with the speed slow cooling of 1 ℃/day, after cooling finishes, can obtain required crystal, crystal is lifted to liquid level, speed with 10 ℃/h is down to room temperature, can obtain fluorine strontium boroberyllate sodium non-linear optic crystal.
Embodiment 5
The growth of NSBBF crystal, adopts molten-salt growth method, and crystal growing apparatus is Resistant heating stove, and temperature controlling instruments is A1-708P type automatic temperature control instrument able to programme.Concrete operations are: select the raw material of NSBBF (the resulting product of embodiment 1) or synthetic corresponding NSBBF compound, then add fusing assistant (B
2o
3, NaF and SrF
2the mixture forming), in following ratio, prepare: 1mole NSBBF or with raw material (the 1.5mole SrCO that synthesizes 1mole NSBBF
3, 3mole BeO, 3mole H
3bO
3, 1mole NaF and 1.3mole SrF
2), then add solubility promoter (0.8moleB
2o
3, 5mole NaF and 0.8mole SrF
2.Put into platinum crucible, then put into Resistant heating stove, with the temperature rise rates of 20 ℃/h, be warming up to 850 ℃, constant temperature is treated the abundant melting of material for 30 hours, be cooled to above 6 ℃ of temperature of saturation, being contained in pyrosol while that seed crystal on seed rod puts into beryllium fluoroborate and fusing assistant counterclockwise single direction rotation seed rod of speed with 45 revs/min; Be cooled to temperature of saturation (770 ℃), then, with the speed slow cooling of 1.5 ℃/day, after cooling finishes, can obtain required crystal, crystal is lifted to liquid level, speed with 15 ℃/h is down to room temperature, can obtain fluorine strontium boroberyllate sodium non-linear optic crystal.
Embodiment 6
The growth of NSBBF crystal, adopts molten-salt growth method, and crystal growing apparatus is homemade Resistant heating stove, and temperature controlling instruments is A1-708P type automatic temperature control instrument able to programme.Concrete operations are: select the raw material of NSBBF (the resulting product of embodiment 1) or synthetic corresponding NSBBF compound, then add fusing assistant (B
2o
3, NaF and SrF
2the mixture forming), in following ratio, prepare: 1mole NSBBF or with raw material (the 1.5mole SrCO that synthesizes 1mole NSBBF
3, 3mole BeO, 3mole H
3bO
3, 1mole NaF, 1.3mole SrF
2), then add solubility promoter (0.7moleB
2o
3, 5mole NaFhe 1mole SrF
2) put into platinum crucible, then put into Resistant heating stove, with the temperature rise rates of 20 ℃/h, be warming up to 850 ℃, constant temperature is treated the abundant melting of material for 30 hours, is cooled to above 8 ℃ of temperature of saturation, being contained in pyrosol while that seed crystal on seed rod puts into beryllium fluoroborate and fusing assistant speed rotary seed crystal rod with 40 revs/min, clockwise direction rotational time is 5 minutes, pause 0.8 minute, then counterclockwise rotate 5 minutes, with this reciprocation cycle; Be cooled to temperature of saturation (770 ℃), then, with the speed slow cooling of 1 ℃/day, after cooling finishes, can obtain required crystal, crystal is lifted to liquid level, speed with 12 ℃/h is down to room temperature, can obtain fluorine strontium boroberyllate sodium non-linear optic crystal.
Embodiment 7
The growth of NSBBF crystal, adopts molten-salt growth method, and crystal growing apparatus is homemade Resistant heating stove, and temperature controlling instruments is A1-708P type automatic temperature control instrument able to programme.Concrete operations are: select the raw material of NSBBF (the resulting product of embodiment 1) or synthetic corresponding NSBBF compound, then add fusing assistant (B
2o
3, NaF and SrF
2the mixture forming), in following ratio, prepare 1mole NSBBF or with synthetic 1mole NSBBF (1.5mole SrCO
3, 3moleBeO, 3mole H
3bO
3, 1mole NaF, 1.3mole SrF
2) raw material, then add solubility promoter 1mole B
2o
3, 4mole NaF, 0.8mole SrF
2.Put into platinum crucible, then put into homemade resistance wire furnace, with the temperature rise rates of 10 ℃/h, be warming up to 850 ℃, constant temperature is treated the abundant melting of material for 40 hours, is cooled to above 10 ℃ of temperature of saturation, being contained in pyrosol while that seed crystal on seed rod puts into beryllium fluoroborate and fusing assistant speed rotary seed crystal rod with 50 revs/min, clockwise direction rotational time is 7 minutes, pause 0.8 minute, then counterclockwise rotate 7 minutes, with this reciprocation cycle; Be cooled to temperature of saturation (780 ℃), then, with the speed slow cooling of 1.2 ℃/day, after cooling finishes, can obtain required crystal, crystal is lifted to liquid level, speed with 10 ℃/h is down to room temperature, can obtain fluorine strontium boroberyllate sodium non-linear optic crystal.
Embodiment 8
The growth of NSBBF crystal, adopts molten-salt growth method, and crystal growing apparatus is homemade Resistant heating stove, and temperature controlling instruments is A1-708P type automatic temperature control instrument able to programme.Concrete operations are: select the raw material of NSBBF (the resulting product of embodiment 1) or synthetic corresponding NSBBF compound, then add fusing assistant (B
2o
3, NaF and SrF
2the mixture forming), in following ratio, prepare: 1mole NSBBF or with raw material (the 1.5mole SrCO that synthesizes 1mole NSBBF
3, 3mole BeO, 3mole H
3bO
3, 1mole NaF, 1.3mole SrF
2), then add solubility promoter 0.7moleB
2o
3, 5mole NaF, 0.8mole SrF
2.Put into platinum crucible, then put into homemade Resistant heating stove, with the temperature rise rates of 10 ℃/h, be warming up to 850 ℃, constant temperature is treated the abundant melting of material for 35 hours, is cooled to above 5 ℃ of temperature of saturation, being contained in pyrosol while that seed crystal on seed rod puts into beryllium fluoroborate and fusing assistant speed rotary seed crystal rod with 60 revs/min, clockwise direction rotational time is 8 minutes, pause 0.5 minute, then counterclockwise rotate 8 minutes, with this reciprocation cycle; Be cooled to temperature of saturation (790 ℃), then, with the speed slow cooling of 1 ℃/day, after cooling finishes, can obtain required crystal, crystal is lifted to liquid level, speed with 10 ℃/h is down to room temperature, can obtain fluorine strontium boroberyllate sodium non-linear optic crystal.
Embodiment 9
Application about NSBBF crystal as frequency-doubling crystal, Fig. 1 is the canonical schema of non-linear optical effect.The frequency of being sent by laser apparatus 1 is the fundamental wave of ω, through reflective mirror 2 and 3, its polarization direction is adjusted to lens direction by half-wave plate 4, pass through again set of lenses 5 and 6, when laser beam passes through to press the NSBBF crystal 7 of certain orientation placement, it is respectively fundamental wave and the frequency doubled light of ω and 2 ω that emergent light has just comprised optical frequency simultaneously, then by dispersing prism 8, the two is separated, thereby obtains the output of frequency doubled light.
Embodiment 10
Use this NSBBF crystal can also realize and frequency, difference frequency output, when frequency is respectively ω
1and ω
2two bundle laser during by certain angle and polarization direction incident and by this NSBBF crystal, can obtain respectively frequency is ω
1+ ω
2, ω
1-ω
2two bundle laser, can obtain so the humorous glistening light of waves of 3 frequencys multiplication, 4 frequencys multiplication or 5 frequencys multiplication.Fig. 2 is the canonical schema of this non-linear optical effect.The fundamental wave of the specific wavelength being sent by laser apparatus 1, through reflective mirror 2 and 3, its polarization direction is adjusted to a direction by half-wave plate 4, then passes through set of lenses 5 and 6, when laser beam passes through to press the NSBBF crystal 7 of certain orientation placement, it is respectively ω that emergent light has just comprised optical frequency simultaneously
1and ω
2and ω
1+ ω
2, ω
1-ω
2the harmonious glistening light of waves of fundamental wave, then separated by dispersing prism 8, thereby obtained the output of the various humorous glistening lights of waves.
In addition, by optical parametric oscillator and photoparametric amplifier device, a branch of pump light is incided after NSBBF crystal, by changing the phase matching angle θ of NSBBF crystal, and obtain the continuously adjustable laser of a branch of its frequency.
Claims (8)
1. a fluorine strontium boroberyllate sodium non-linear optic crystal, its molecular formula is NaSr
3be
3b
3o
9f
4, belonging to trigonal system, spacer is R3m, fusing point is 850 ℃, deliquescence not in air, molecular weight is 565.31, cell parameter is
α=β=90 °, γ=120 °,
z=3.
2. a molten-salt growth method for fluorine strontium boroberyllate sodium non-linear optic crystal described in claim 1, its concrete steps are as follows:
(1) within putting into the platinum crucible of crystal growing furnace after fluorine strontium boroberyllate sodium and fusing assistant being mixed in proportion evenly, with the temperature rise rates of 10～30 ℃/h, be heated to 850 ℃, constant temperature 10～40 hours, be cooled to again on temperature of saturation 2～10 ℃, obtain the pyrosol of fluorine-containing strontium boroberyllate sodium compound and fusing assistant;
The molecular formula of described fluorine strontium boroberyllate sodium compound is NaSr
3be
3b
3o
9f
4;
Described fusing assistant is B
2o
3, NaF and SrF
2the mixture forming;
The mol ratio of described fluorine strontium boroberyllate sodium and fusing assistant is NaSr
3be
3b
3o
9f
4: B
2o
3: NaF:SrF
2=1:(0.5～1): (3.5～5): (0.4～1);
(2) being contained in seed crystal on seed rod, from crystal growing furnace top, put into fluorine-containing strontium boroberyllate sodium compound that above-mentioned steps (1) obtains and the pyrosol of fusing assistant, simultaneously with the speed rotary seed crystal rod of 10-100 rev/min, be cooled to temperature of saturation, then with the speed of 0.5～1.5 ℃/day, lower the temperature, after cooling finishes, gained crystal is lifted to liquid level, and be down to room temperature with the speed of 5～15 ℃/h, obtain fluorine strontium boroberyllate sodium non-linear optic crystal, its molecular formula is NaSr
3be
3b
3o
9f
4.
3. by the molten-salt growth method of fluorine strontium boroberyllate sodium non-linear optic crystal claimed in claim 2, it is characterized in that described NaSr
3be
3b
3o
9f
4compound employing solid phase synthesis process at high temperature sintering obtains, and its reaction equation is:
3SrCO
3+6BeO+6H
3BO
3+2NaF+3SrF
2＝2NaSr
3Be
3B
3O
9F
4+3CO
2↑+9H
2O↑
Or: 3SrCO
3+ 6BeO+3B
2o
3+ 2NaF+3SrF
2=2NaSr
3be
3b
3o
9f
4+ 3CO
2↑.
4. by the molten-salt growth method of fluorine strontium boroberyllate sodium non-linear optic crystal claimed in claim 2, it is characterized in that, in described step (2), the sense of rotation of seed rod is single direction rotation or bidirectional reversible rotation.
5. by the molten-salt growth method of fluorine strontium boroberyllate sodium non-linear optic crystal claimed in claim 4, it is characterized in that, each the one direction rotational time in described bidirectional reversible rotation is 1-10 minute; The timed interval of adjacent two one directions rotation is 0.5-1 minute.
6. a purposes for fluorine strontium boroberyllate sodium non-linear optic crystal claimed in claim 1, is characterized in that: the harmonic wave light output device that it is realized 2 frequencys multiplication, 3 frequencys multiplication, 4 frequencys multiplication, 5 frequencys multiplication or 6 frequencys multiplication for the preparation of the laser beam that to wavelength X is 1.064 μ m and is shorter than the humorous glistening light of waves output of 200nm.
7. by the purposes of fluorine strontium boroberyllate sodium non-linear optic crystal claimed in claim 6, it is characterized in that: described harmonic wave light output device is harmonic generator, optical parametric oscillation and photoparametric amplifier part or fiber waveguide device for ultraviolet region.
8. by the purposes of fluorine strontium boroberyllate sodium non-linear optic crystal claimed in claim 7, it is characterized in that: described harmonic generator is optical parametric oscillation and amplifying device from infrared to ultraviolet region.
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| WO2017054347A1 (en) * | 2015-09-29 | 2017-04-06 | 中国科学院福建物质结构研究所 | Nonlinear optical crystal beryllium fluoroboarate and preparation method and application thereof |
| US11898267B2 (en) | 2015-09-29 | 2024-02-13 | Fujian Institute Of Research On The Structure Of Matter, Chinese Academy Of Sciences | Nonlinear optical crystal fluorine boron beryllium salt and its preparation process and use |
| CN108018606A (en) * | 2016-11-04 | 2018-05-11 | 中国科学院理化技术研究所 | RbZn2BO3Cl2Nonlinear optical crystal and preparation method and application thereof |
| CN112575369A (en) * | 2019-09-30 | 2021-03-30 | 天津理工大学 | Compound cesium chloroborozincate and cesium chloroborozincate nonlinear optical crystal as well as preparation method and application thereof |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5343827A (en) * | 1992-02-19 | 1994-09-06 | Crystal Technology, Inc. | Method for crystal growth of beta barium boratean |
| CN101050547A (en) * | 2006-04-07 | 2007-10-10 | 中国科学院理化技术研究所 | Method for growing potassium/sodium fluoroboroberyllate single crystals by hydrothermal method |
| CN101050543A (en) * | 2006-04-07 | 2007-10-10 | 中国科学院理化技术研究所 | Method for growing rubidium fluoroboroberyllate/cesium monocrystal by hydrothermal method |
| WO2008034283A1 (en) * | 2006-09-15 | 2008-03-27 | Technical Institute Of Physics And Chemistry Chinese Academy Of Sciences | Beryllium borate fluoride salt nonlinear optical crystal, its growth method and uses |
| CN101200809A (en) * | 2006-12-12 | 2008-06-18 | 中国科学院理化技术研究所 | Method for synthesizing single-phase polycrystalline powder of fluoroboroberberic acid salt |
-
2011
- 2011-06-15 CN CN201110159659.8A patent/CN102828246B/en not_active Expired - Fee Related
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5343827A (en) * | 1992-02-19 | 1994-09-06 | Crystal Technology, Inc. | Method for crystal growth of beta barium boratean |
| CN101050547A (en) * | 2006-04-07 | 2007-10-10 | 中国科学院理化技术研究所 | Method for growing potassium/sodium fluoroboroberyllate single crystals by hydrothermal method |
| CN101050543A (en) * | 2006-04-07 | 2007-10-10 | 中国科学院理化技术研究所 | Method for growing rubidium fluoroboroberyllate/cesium monocrystal by hydrothermal method |
| WO2008034283A1 (en) * | 2006-09-15 | 2008-03-27 | Technical Institute Of Physics And Chemistry Chinese Academy Of Sciences | Beryllium borate fluoride salt nonlinear optical crystal, its growth method and uses |
| CN101200809A (en) * | 2006-12-12 | 2008-06-18 | 中国科学院理化技术研究所 | Method for synthesizing single-phase polycrystalline powder of fluoroboroberberic acid salt |
Non-Patent Citations (4)
| Title |
|---|
| 一种潜在的新型非线性光学材料-氟硼酸铍;夏文兵等;《人工晶体学报》;20050831;第34卷(第4期);8-12 * |
| 夏文兵等.一种潜在的新型非线性光学材料-氟硼酸铍.《人工晶体学报》.2005,第34卷(第4期),580、597-600. * |
| 张建秀等.氟硼铍酸钾晶体的生长、表面形貌和缺陷.《人工晶体学报》.2003,第32卷(第1期),8-12. * |
| 氟硼铍酸钾晶体的生长、表面形貌和缺陷;张建秀等;《人工晶体学报》;20030228;第32卷(第1期);580、597-600 * |
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