CN101798707B - Nonlinear optical crystal BaMgBO3F, preparation method and application thereof - Google Patents
Nonlinear optical crystal BaMgBO3F, preparation method and application thereof Download PDFInfo
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- CN101798707B CN101798707B CN200910077443XA CN200910077443A CN101798707B CN 101798707 B CN101798707 B CN 101798707B CN 200910077443X A CN200910077443X A CN 200910077443XA CN 200910077443 A CN200910077443 A CN 200910077443A CN 101798707 B CN101798707 B CN 101798707B
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- barium fluoborate
- linear optic
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- 239000013078 crystal Substances 0.000 title claims abstract description 119
- 230000003287 optical effect Effects 0.000 title claims abstract description 19
- 238000002360 preparation method Methods 0.000 title claims abstract description 11
- 230000000694 effects Effects 0.000 claims abstract description 10
- 238000001816 cooling Methods 0.000 claims abstract description 7
- 238000000354 decomposition reaction Methods 0.000 claims abstract description 4
- 239000011777 magnesium Substances 0.000 claims description 60
- 229910052749 magnesium Inorganic materials 0.000 claims description 42
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 41
- 229910052788 barium Inorganic materials 0.000 claims description 37
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 claims description 31
- 229910016036 BaF 2 Inorganic materials 0.000 claims description 16
- 238000006243 chemical reaction Methods 0.000 claims description 10
- 229910052731 fluorine Inorganic materials 0.000 claims description 9
- 230000004907 flux Effects 0.000 claims description 9
- 150000001875 compounds Chemical class 0.000 claims description 8
- 238000002109 crystal growth method Methods 0.000 claims description 8
- 239000007787 solid Substances 0.000 claims description 8
- 150000001552 barium Chemical class 0.000 claims description 6
- 239000000126 substance Substances 0.000 claims description 5
- 241000931526 Acer campestre Species 0.000 claims description 4
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims description 4
- 150000001553 barium compounds Chemical class 0.000 claims description 4
- 229910052796 boron Inorganic materials 0.000 claims description 4
- 238000000034 method Methods 0.000 claims description 4
- 239000007864 aqueous solution Substances 0.000 claims description 3
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 claims 1
- 239000011737 fluorine Substances 0.000 claims 1
- 239000012071 phase Substances 0.000 abstract description 13
- 239000000155 melt Substances 0.000 abstract description 5
- 238000010438 heat treatment Methods 0.000 abstract description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 2
- IJBYNGRZBZDSDK-UHFFFAOYSA-N barium magnesium Chemical compound [Mg].[Ba] IJBYNGRZBZDSDK-UHFFFAOYSA-N 0.000 abstract 3
- 239000003795 chemical substances by application Substances 0.000 abstract 1
- 238000002156 mixing Methods 0.000 abstract 1
- 239000007790 solid phase Substances 0.000 abstract 1
- 230000007704 transition Effects 0.000 abstract 1
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 26
- 238000005303 weighing Methods 0.000 description 14
- 229910052697 platinum Inorganic materials 0.000 description 13
- 239000000306 component Substances 0.000 description 12
- 239000000203 mixture Substances 0.000 description 12
- 239000000843 powder Substances 0.000 description 12
- 239000003153 chemical reaction reagent Substances 0.000 description 11
- 239000007788 liquid Substances 0.000 description 8
- 239000000463 material Substances 0.000 description 8
- 239000002994 raw material Substances 0.000 description 8
- 238000003756 stirring Methods 0.000 description 5
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- 238000000227 grinding Methods 0.000 description 4
- 239000004570 mortar (masonry) Substances 0.000 description 4
- 238000005245 sintering Methods 0.000 description 4
- 229910052761 rare earth metal Inorganic materials 0.000 description 3
- 229910019440 Mg(OH) Inorganic materials 0.000 description 2
- AYJRCSIUFZENHW-UHFFFAOYSA-L barium carbonate Chemical compound [Ba+2].[O-]C([O-])=O AYJRCSIUFZENHW-UHFFFAOYSA-L 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 230000010287 polarization Effects 0.000 description 2
- 230000001737 promoting effect Effects 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 238000010583 slow cooling Methods 0.000 description 2
- 238000012546 transfer Methods 0.000 description 2
- RILZRCJGXSFXNE-UHFFFAOYSA-N 2-[4-(trifluoromethoxy)phenyl]ethanol Chemical class OCCC1=CC=C(OC(F)(F)F)C=C1 RILZRCJGXSFXNE-UHFFFAOYSA-N 0.000 description 1
- 241000024287 Areas Species 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- LDDQLRUQCUTJBB-UHFFFAOYSA-N ammonium fluoride Chemical compound [NH4+].[F-] LDDQLRUQCUTJBB-UHFFFAOYSA-N 0.000 description 1
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical group OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000008358 core component Substances 0.000 description 1
- 239000002178 crystalline material Substances 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 230000004927 fusion Effects 0.000 description 1
- 238000009434 installation Methods 0.000 description 1
- 239000008204 material by function Substances 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 230000005693 optoelectronics Effects 0.000 description 1
- 230000010355 oscillation Effects 0.000 description 1
- 150000002910 rare earth metals Chemical class 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 231100000004 severe toxicity Toxicity 0.000 description 1
- 238000004513 sizing Methods 0.000 description 1
- 238000010532 solid phase synthesis reaction Methods 0.000 description 1
- 125000006850 spacer group Chemical group 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
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Abstract
A barium magnesium fluoborate nonlinear optical crystal, its preparation method and application, its unit cell parameter is a ═ 17.59
b＝30.50
c＝8.05
α＝β＝γ＝90，Z＝48；Mg2+4O is coordinated with 2F; the solid-solid phase transition temperature is 900 +/-10 ℃, and the low-temperature phase has a frequency doubling effect and allows ultraviolet or deep ultraviolet band light beams to penetrate through; the high-temperature phase frequency doubling effect is zero; the decomposition temperature is 1050 ℃; does not deliquesce in the air; is insoluble in water solution with pH value of 2-12 at normal temperature; the preparation method comprises the following steps: mixing barium magnesium fluoborate with a fluxing agent and heating to form a melt; seed crystals are seeded at a temperature of 0.5 to 5 ℃ above the temperature of the saturation point of the melt; then reducing the temperature to 0-1 ℃ below the saturation point temperature while rotatingCooling to grow crystal; growing the crystal to a required size, extracting the crystal from the melt, and cooling to room temperature to obtain a barium magnesium fluoborate single crystal; the crystal may be used as a frequency doubling crystal in an optical parametric oscillator or a harmonic generator.
Description
Technical field
The present invention relates to the optoelectronic functional materials field, particularly inorganic nonlinear optical crystal material and artificial crystal growth field, " inorganic ", " nonlinear optics ", " crystal " correspond respectively to the ownership of material aspect three of compositions, application, state.Particularly, be that chemical formula is BaMgBO
3The crystalline material of F (being called for short BMBF) and growth method thereof and of the application of this material as non-linear optic crystal.
Background technology
Directly producing laser by laser apparatus, often can only produce the laser of specific wavelength, is 1064nm like the Nd:YAG Wavelength of Laser, is infrared laser.Utilize non-linear optical effect, can double the frequency of laser or regulate continuously, thereby wavelength shortens, even wavelength is reduced to below the 200nm, promptly obtain visible, ultraviolet, deep ultraviolet laser.Wavelength of Laser shortens; Mean littler coherence length; Higher single photon energy; This has conclusive effect for the raising of technology such as the information storage of utilizing laser to carry out, precision sizing, microcosmic detection, micromanagement, and is significant to Application Areass such as instrument research and development, biological medicine, military affairs.Non-linear optic crystal is realized the core component of above-mentioned non-linear optical effect just.
The non-linear optic crystal of practicability is mainly at present: the KTiOPO that is used for the output of Nd:YAG laser 2 frequencys multiplication
4(being called for short KTP), be used for the LiB that Nd:YAG laser 3 frequencys multiplication are exported
3O
5(being called for short LBO), be used for β-BaB that Nd:YAG laser 2 to 5 frequencys multiplication are exported
2O
4(being called for short BBO).
BaMgBO
3F (be called for short BMBF) belongs to fluoroboric acid salt material on elementary composition, this type material as non-linear optic crystal research and to some extent report still have following 4 kinds: KBBF class (KBe
2BO
3F
2, K can partly or entirely be replaced by other alkali metal), CBF class (Ca
5(BO
3)
3F, Ca and F with 1: 1 dosage than partly or entirely being replaced by REE and O simultaneously), BaAlBO
3F
2(being called for short BABF) and BaCaBO
3F (being called for short BCBF).
The above several kinds of non-linear optical crystal material respectively has certain defective.BBO and LBO influence the generation deliquescence because of receiving water vapour, can not under high humidity environment, use for a long time, and wherein BBO is again more deliquescent; The KTP laser damage threshold is little, and the ultraviolet cut-on side wave is long only to arrive about 350nm (referring to Journal of Crystal Growth 310 (2008) 2010-2014), thereby only limits to be used in the 2 frequencys multiplication output of Nd:YAG laser; KBBF contains toxic stronger Be element, and the getable crystalline size of institute is more limited, thereby its growth, uses inconvenience and restriction are all arranged; CBF fails to realize the phase matched output of direct 4 frequencys multiplication of Nd:YAG laser because of the reason of specific refractory power, still uses and mode (referring to OPTICS EXPRESS Vol.16 such as Xu Ke, No.22 (27October 2008) 17735-17744) frequently; BABF (referring to Optical Meterials 26 (2004) 421-423) and BCBF are (referring to D.A.Keszler; Et al.New Borate Structure for NLOApplication; In:Proc.1994 Meter.Res.Soc.Conf., 1994,15-22 and Journalof Crystal Growth 289 (2006) 188-191) nonlinear optical property report to some extent; But be used to realize Nd:YAG laser 3 frequencys multiplication, the output of 4 frequencys multiplication about them, do not see the report that explicit data is arranged.
(US Patent No.5 such as Keszler; 677,921) also reported the application of adulterated Yb:BCBF crystal as laser crystals, this laser crystals has the performance of non-linear optic crystal simultaneously; Thereby can be used as the self-frequency-doubling crystal, and as promoting and deriving and point out the Ba in the matrix
2+, Ca
2+Substitute by other divalent-metal ion, comprising Mg
2+, what practical application is not arranged during doped with rare-earth elements but declare material B MBF.
The present invention is directed to not rare earth doped BMBF, in addition, the related experiment data of this patent show BMBF that this patent relates to not in BCBF derives the scope of promoting, and the two all has tangible difference in structure, properties:
BCBF 1083.4 ℃ with the composition fusion, and BMgBF can decompose at 1050 ℃, BMBF remains in phase transformation about 900 ℃, wherein low temperature has the frequency-doubled effect approaching with KDP mutually, and the frequency-doubled effect of high temperature phase obviously diminishes and almost do not have;
Among the BCBF, Ca
2+By 5 O and 2 F coordinations, and the Mg among the corresponding BMBF
2+, be in mutually by 4 O and 2 F coordinations at low temperature;
BCBF belongs to the P-62m spacer; Unit cell parameters is a=9.049
; C=4.326
; Z=3; And BMBF a=17.59
; B=30.50
; C=8.05
; α=β=γ=90 °, Z=48;
BMBF compares with BCBF, and the ultraviolet cut-on limit of BMBF is shorter, means that the application band of BMBF can be to more short wavelength's direction expansion, and 4 frequencys multiplication that particularly can realize Nd:YAG laser are the phase matched output of the laser of wavelength 266nm.
The BaMgBO that the present invention relates to
3The F crystal not deliquescence, can realize the 4 frequency multiplication phase matched output of Nd:YAG laser, therefore be a kind of brand-new non-linear optical crystal material that anti-deliquescence advantage is arranged.
Summary of the invention
The object of the present invention is to provide chemical formula is BaMgBO
3The non-linear optic crystal of F, this non-linear optic crystal can allow ultraviolet, good the seeing through of deep ultraviolet wave band light beam, and the solid-solid phase-change temperature is 900 ± 10 ℃, and wherein low temperature has the frequency-doubled effect approaching with KDP mutually.
Another object of the present invention is to provide a kind of non-linear optic crystal BaMgBO
3The flux growth method of F;
A purpose more of the present invention is for providing non-linear optic crystal BaMgBO
3The purposes of F, it is for as frequency-doubling crystal, and that the laser that laser apparatus is directly produced is converted into is visible, ultraviolet and deep ultraviolet laser, 4 frequencys multiplication that particularly can phase matched output Nd:YAG laser.
Technical scheme of the present invention is following:
Barium fluoborate magnesium non-linear optic crystal provided by the invention, its chemical formula is BaMgBO
3F, its unit cell parameters is a=17.59
, b=30.50
, c=8.05
, α=β=γ=90 °, Z=48; Mg in the crystal
2+By 4 O and 2 F coordinations; The solid-solid phase-change temperature is 900 ± 10 ℃, and low temperature has frequency-doubled effect mutually, allows ultraviolet or deep ultraviolet wave band light beam to see through; High temperature phase frequency-doubled effect is zero; Decomposition temperature is 1050 ℃; Deliquescence not in air; Be insoluble to the aqueous solution of pH value 2-12 under the normal temperature.
It is barium fluoborate magnesium non-linear optic crystal growth method that the present invention provides, and it is a flux growth method, and its step is following:
(1) powdery barium fluoborate magnesium and fusing assistant are mixed, be heated to 800-900 ℃, leave standstill or to be stirred to melt even, must contain the mixed melt of barium fluoborate magnesium and fusing assistant;
Said fusing assistant is BaO-LiF-B
2O
3-BF
3System fusing assistant or BaO-NaF-B
2O
3-BF
3The system fusing assistant;
When said fusing assistant is BaO-LiF-B
2O
3-BF
3During the system fusing assistant, the mol ratio of each component is in said barium fluoborate magnesium and the said fusing assistant:
BMBF∶Ba∶B∶F∶Li＝(0.8-1.5)∶(0.12-0.3)∶(0.75-1.2)∶(0.6-1)∶(0-1.5)；
When fusing assistant is BaO-NaF-B
2O
3-BF
3During the system fusing assistant, the mol ratio of each component is in said barium fluoborate magnesium and the said fusing assistant:
BMBF∶Ba∶B∶F∶Na＝(0.8-1.5)∶(0-0.3)∶(0.6-1.5)∶(0.6-2.7)∶(0.4-1.5)；
(2) through attempting confirming the saturation point temperature of above-mentioned mixed melt, said saturation point temperature is no more than 950 ℃;
The mixed melt temperature is set on the saturation point temperature 0.5-5 ℃, following seed crystal: seed crystal is fixed on the seed rod end, seed crystal is stretched into from the reactors top, make itself and mixed melt surface contact or stretch in the mixed melt; In the time of following seed crystal 0-30 minute, cool the temperature under the saturation point temperature 0-1 ℃, beginning is with 0-40 rev/min of rotating speed rotation seed crystal, and begins cooling with 0.05-5 ℃ of/day rate of temperature fall, and crystal is grown up gradually; When crystal is grown up to desired size, crystal is lifted from mixed melt, with 2-50 ℃ of/hour speed furnace temperature is reduced to room temperature then, obtain barium fluoborate magnesium monocrystalline.
Described barium fluoborate magnesium is prepared by the arbitrary reaction formula in the reactions formula:
2BaO+MgF
2+MgO+B
2O
3→2BaMgBO
3F
2MgO+BaF
2+BaO+B
2O
3→2BaMgBO
3F
In these two reaction formula
BaO can use BaCO
3, Ba (OH)
2Or BaC
2O
4Substitute;
BaCO
3→BaO+CO
2↑
Ba(OH)
2→BaO+H
2O↑
BaC
2O
4→BaO+CO
2↑+CO↑
MgO can use Mg (CO
3)
4Mg (OH)
25H
2O, Mg (OH)
2Or MgC
2O
4Substitute;
Mg(CO
3)
4·Mg(OH)
2·5H
2O→MgO+CO
2+H
2O
Mg(OH)
2→MgO+H
2O↑
MgC
2O
4→MgO+CO
2↑+CO↑
B
2O
3Available H
3BO
3Substitute.
2H
3BO
3→B
2O
3+3H
2O↑
Above-mentioned each surrogate produces component required for the present invention when reacting by heating, and unwanted component is overflowed voluntarily;
Said barium fluoborate magnesium is substituted by fluorochemicals, boron-containing compound, containing barium compound and the magnesium-containing compound with mol ratio.
Said fluorochemicals is MgF
2, BaF
2, NH
4F or NH
4HF
2
Said boron-containing compound is B
2O
3Or H
3BO
3
Said containing barium compound is BaO, BaCO
3, BaF
2, Ba (OH)
2, BaC
2O
4Or Ba (NO
3)
2
Said magnesium-containing compound is MgO, Mg (CO
3)
4Mg (OH)
25H
2O, MgF
2, Mg (OH)
2, MgC
2O
4Or Mg (NO
3)
2
Said BaO-LiF-B
2O
3-BF
3The system fusing assistant is to choose BaCO by identical mol ratio
3, Ba (OH)
2, BaF
2, BaC
2O
4, Ba (NO
3)
2, Li
2CO
3, LiF, B
2O
3, H
3BO
3, NH
4F, NH
4HF
2In 3 to 11 kinds of preparations.
Said BaO-LiF-B
2O
3-BF
3The system fusing assistant is to choose BaCO by identical mol ratio
3, Ba (OH)
2, BaF
2, BaC
2O
4, Ba (NO
3)
2, Na
2CO
3, NaF, B
2O
3, H
3BO
3, NH
4F, NH
4HF
2In 3 to 11 kinds of preparations.
The purposes of barium fluoborate magnesium non-linear optic crystal of the present invention is: this barium fluoborate magnesium non-linear optic crystal is used as frequency-doubling crystal in harmonic generator, and conversion optical maser wavelength produces the laser of visible light to deep ultraviolet wave band.
The purposes of barium fluoborate magnesium non-linear optic crystal of the present invention can be: the laser of 4 frequency multiplication wavelength 266nm of the phase matched output Nd:YAG laser of this barium fluoborate magnesium non-linear optic crystal.
The purposes of barium fluoborate magnesium non-linear optic crystal of the present invention also can be: this barium fluoborate magnesium non-linear optic crystal is used as frequency-doubling crystal in optical parametric oscillator, and conversion optical maser wavelength produces the laser of visible light to deep ultraviolet wave band.
Advantage of the present invention is following:
Have certain non-linear optical effect and can make ultraviolet, good the seeing through of dark purple external enwergy band of light bundle, so the laser of 4 frequency multiplication wavelength 266nm of ability phase matched output Nd:YAG laser; Do not contain the Be element of severe toxicity in elementary composition, safer to human body; Deliquescence can not use in wet environment for a long time yet; Chemical property is stable, and is insoluble in the aqueous solution of pH2-12; But withstand high temperatures, solid-solid phase-change temperature are 900 ± 10 ℃, and decomposition temperature is 1050 ℃.
Description of drawings
Fig. 1: BaMgBO
3The crystalline structure figure of F;
Fig. 2: BaMgBO
3The X ray diffracting spectrum of F powder (Cu, K
α)
Fig. 3: non-linear optic crystal is as the synoptic diagram of the frequency doubling device in the harmonic generator
1 is half-wave plate; 2,3 form set of lenses; 4 is the frequency-doubling crystal device; 5 is dispersing prism.
Fig. 4: non-linear optic crystal is as the synoptic diagram of the frequency doubling device in the optical parameter oscillator
1 is half-wave plate; 2,3 form set of lenses; 4 frequency-doubling crystal devices; 5 dispersing prisms; 6,7 form resonator cavity.
Embodiment
Embodiment 1-2 is a BMBF powder solid phase synthesis:
Take by weighing following reagent:
BaCO
31.973 gram closes 0.01mol;
BaF
21.753 gram closes 0.01mol;
MgO 0.806 gram closes 0.02mol;
H
3BO
31.236 gram closes 0.02mol;
With claim reagent (mole proportioning be BaCO
3: BaF
2: MgO: H
3BO
3=1: 1: 2: 2) place the agate mortar grinding of 11 centimetres of internal diameters it to be mixed in 10 minutes; Then mix powder is transferred in the platinum crucible, places the pre-burning of retort furnace internal heating again; Calcined temperature is 650 ℃, 3 hours time; Take out crucible then, will be wherein regrinding 10 minutes in solid transfer to the agate mortar.After the grinding powder is packed in the crucible once more, place retort furnace heat-agglomerating; Sintering temperature is 800 ℃, 15 hours time; Be BZBF low temperature phase powder behind the sintering gained solid abrasive.
Take by weighing following reagent:
BaC
2O
42.253 gram closes 0.01mol;
Ba (OH)
21.713 gram closes 0.01mol;
5MgO4CO
26H
2O 1.943 grams close 0.004mol;
NH
4HF
20.571 gram closes 0.01mol;
B
2O
30.696 gram closes 0.01mol;
With claim reagent (mole proportioning be BaC
2O
4: Ba (OH)
2: 5MgO4CO
26H
2O: NH
4HF
2: B
2O
3=10: 10: 4: 10: 10) place the agate mortar grinding of 13 centimetres of internal diameters it to be mixed in 8 minutes; Then mix powder is transferred in the platinum crucible, places the pre-burning of retort furnace internal heating again.Calcined temperature is 600 ℃, 3 hours time; Take out crucible then, will be wherein regrinding 15 minutes in solid transfer to the agate mortar; After the grinding powder is packed in the crucible once more, place retort furnace heat-agglomerating; Sintering temperature is 950 ℃, 10 hours time.Be BMBF high temperature phase powder behind the sintering gained solid abrasive.
Embodiment 3-8 is the growth of BMBF crystalline
Take by weighing the BaMgBO of embodiment 1 or 2 preparations
3The F powder: 191.3 grams close 0.8mol
Take by weighing following flux components:
BaF
252.6 gram closes 0.3mol
LiF 10.4 grams close 0.4mol
H
3BO
374.196 gram closes 1.2mol
Li
2CO
336.82 gram closes 0.5mol
Above-mentioned all reagent mix evenly are placed in the platinum crucible, place in the crystal growing furnace; Be heated to 800 ℃ make raw material all melt mixed melt, leave standstill until mixed melt limpid evenly; After attempting confirming its saturation point temperature, the mixed melt temperature is set on the saturation point temperature 0.5 ℃, seed crystal is fixed on the seed rod end, then it is lowered in the mixed melt; Seed crystal is lowered to behind the melt temperature is set under the saturation point 0.2 ℃, rotates seed crystal immediately, 40 rev/mins of rotating speeds, and slowly cooling of beginning, and rate of temperature fall is 5 ℃/day, then crystal is grown up gradually; Treat that crystalline size grows into Φ 35mm*10mm crystal is lifted from melt liquid level, with 50 ℃/hour speed furnace temperature is reduced to room temperature then, obtain the BaMgBOF of present embodiment
3Monocrystalline.
Take by weighing the BaMgBO of embodiment 1 or 2 preparations
3The F powder: 239.1 grams close 1mol
Take by weighing following flux components:
BaCO
331.6 gram closes 0.16mol
LiF 20.8 grams close 0.8mol
B
2O
334.8 gram closes 0.5mol
Above-mentioned all reagent mix evenly are placed in the platinum crucible, place in the crystal growing furnace; At first be heated to 850 ℃ make raw material all melt mixed melt, stir until mixed melt limpid evenly with platinum whisking appliance rotation then; Take out whisking appliance, after attempting confirming its saturation point temperature, the mixed melt temperature be set on the saturation point temperature 1 ℃, seed crystal is fixed on the seed rod end, then with it slowly down to contact mixed melt liquid level; Seed crystal is lowered to after the mixed melt 15 minutes, cools the temperature to the saturation point temperature, begins to rotate seed crystal, 25 rev/mins of rotating speeds, and slowly cooling of beginning, and rate of temperature fall is 0.5 ℃/day, then crystal is grown up gradually; Treat that crystalline size grows into Φ 30mm*8mm, crystal is lifted from the mixed melt liquid level, with 20 ℃ of/hour speed furnace temperature is reduced to room temperature then, obtain the BaMgBOF of present embodiment
3Monocrystalline.
Take by weighing the BaMgBO of embodiment 1 or 2 preparations
3The F powder: 358.6 grams, close 1.5mol
Take by weighing following flux components:
BaF
221 grams close 0.12
H
3BO
346.37 gram closes 0.75
NH
4HF
220.52 gram closes 0.36
Above-mentioned all reagent mix evenly are placed in the platinum crucible, place in the crystal growing furnace; At first be heated to 900 ℃ make raw material all melt mixed melt, stir until melt limpid evenly with platinum whisking appliance rotation then; Take out whisking appliance, after attempting confirming its saturation point temperature, the mixed melt temperature is set to supreme 5 ℃ of saturation point temperature, seed crystal is fixed on the seed rod end, slowly be lowered to it in melt then; Seed crystal is lowered to behind the melt 5 minutes, cools the temperature to the saturation point temperature to following 1 ℃, leaves standstill seed crystal and begins slow cooling, and rate of temperature fall is 0.05 ℃/day, and then crystal is grown up gradually; Treat that crystalline size grows into Φ 25mm*12mm, crystal is lifted from the mixed melt liquid level, with 2 ℃/hour speed furnace temperature is reduced to room temperature then, promptly obtain the BaMgBOF of present embodiment
3Monocrystalline.
Taking by weighing following raw material is the BMBF component:
BaCO
3157.84 gram closes 0.8mol
MgO 16.121 grams close 0.4mol
MgF
224.924 gram closes 0.4mol
B
2O
327.848 gram closes 0.4mol
Take by weighing following flux components:
BaF
252.6 gram closes 0.3mol
NaF 63 grams close 1.5mol
H
3BO
392.7 gram closes 1.5mol
NH
4HF
217.1 gram closes 0.3mol
Above-mentioned all reagent mix evenly are placed in the platinum crucible, place in the crystal growing furnace; At first be heated to 830 ℃ make raw material all melt mixed melt, be lowered to platinum whisking appliance rotation then and stir until mixed melt limpid evenly; Take out whisking appliance, after attempting confirming its saturation point temperature, the mixed melt temperature be set on the saturation point temperature 2 ℃, seed crystal is fixed on the seed rod end, then with it slowly down to contact mixed melt liquid level; Seed crystal is lowered to after the mixed melt 10 minutes, cools the temperature to saturation point to following 0.6 ℃, begins to rotate seed crystal, 30 rev/mins of rotating speeds, and slowly cooling of beginning, and rate of temperature fall is 3 ℃/day, then crystal is grown up gradually; Treat that crystalline size grows into 35mm*25mm*12mm, crystal is lifted from melt liquid level, with 35 ℃/hour speed furnace temperature is reduced to room temperature then, promptly obtain the BaMgBOF of present embodiment
3Monocrystalline.
Taking by weighing following raw material is the BMBF component:
BaCO3 197.3 grams close 1mol
MgO 40.3 grams close 1mol
NH4F 37.1 grams close 1mol
B2O3 69.6 grams close 0.5mol
Taking by weighing following reagent is flux components:
BaF
228.0 gram closes 0.16mol
NaF 33.6 grams close 0.8mol
H
3BO
361.83 gram closes 1mol
Above-mentioned all reagent mix evenly are placed in the platinum crucible, place in the crystal growing furnace; At first be heated to 870 ℃ make raw material all melt mixed melt, be lowered to platinum whisking appliance rotation then and stir until mixed melt limpid evenly; Take out whisking appliance, after attempting confirming its saturation point temperature, the mixed melt temperature is set on the saturation point temperature 3 ℃, seed crystal is fixed on the seed rod end, slowly be lowered to it in mixed melt then; Seed crystal is lowered to after the mixed melt 8 minutes, cools the temperature to below the saturation point 0.4 ℃, begins to rotate seed crystal, 20 rev/mins of rotating speeds, and slowly cooling of beginning, and rate of temperature fall is 0.3 ℃/day, then crystal is grown up gradually; Treat that crystalline size grows into 25mm*20*10mm crystal is lifted from the mixed melt liquid level, with 10 ℃/hour speed furnace temperature is reduced to room temperature then, promptly obtain the BaMgBOF of present embodiment
3Monocrystalline.
Embodiment 8
Take by weighing the BaMgBO of embodiment 1 or 2 preparations
3The F powder: 358.6 grams close 1.5mol
Take by weighing following flux components:
NaF 16.8 grams close 0.4mol
H
3BO
337.1 gram closes 0.6mol
NH
4HF
25.7 gram closes 0.1mol
Above-mentioned all reagent mix evenly are placed in the platinum crucible, place in the crystal growing furnace; At first be heated to 900 ℃ make raw material all melt mixed melt, be lowered to platinum whisking appliance rotation then and stir until mixed melt limpid evenly; Take out whisking appliance, after attempting confirming its saturation point temperature, the mixed melt temperature is set on the saturation point temperature 5 ℃, seed crystal is fixed on the seed rod end, slowly be lowered to it in mixed melt then; Seed crystal is lowered to after the mixed melt 5 minutes, cools the temperature under the saturation point temperature 1 ℃, leaves standstill seed crystal and begins slow cooling, and rate of temperature fall is 0.05 ℃/day, and then crystal is grown up gradually; Treat that crystalline size grows into 20mm*20mm*15mm, crystal is lifted from the mixed melt liquid level, with 2 ℃/hour speed furnace temperature is reduced to room temperature then, promptly obtain the BaMgBOF of present embodiment
3Monocrystalline.
Embodiment 9
BMBF crystal of the present invention is used for the frequency-doubling crystal device of harmonic generator:
The BMBF crystal that above-mentioned arbitrary embodiment is obtained is installed in the position of label 4 among Fig. 3; Then frequency is that the fundamental frequency light of ω is behind half-wave plate 1 adjustment polarization direction; Set of lenses 2,3 boundlings again, incident and through frequency-doubling crystal device 4 (crystal of the present invention) then, then a part of fundamental frequency phototransformation is that frequency is the frequency doubled light of 2 ω; Make the beam separation of different frequency again by dispersing prism, promptly obtain unicolor frequency doubled light.
The BMBF crystal is used as the frequency-doubling crystal device in the optical parametric oscillator:
The position of label 4 in the BMBF crystal installation plan that above-mentioned arbitrary embodiment is obtained; Then frequency is that the fundamental frequency light of ω is behind half-wave plate 1 adjustment polarization direction; Set of lenses 2,3 boundlings again; Incide then in the resonator cavity 6,7, repeated oscillation is also passed through frequency-doubling crystal device 4 (crystal of the present invention), and then a part of fundamental frequency phototransformation is that frequency is ω
1+ ω
2And ω
1-ω
2Light, make the beam separation of different frequency again by dispersing prism, obtaining frequency respectively is ω
1+ ω
2And ω
1-ω
2Light.
Claims (12)
1. barium fluoborate magnesium non-linear optic crystal, its chemical formula is BaMgBO
3F, its unit cell parameters does
α=β=γ=90 °, Z=48; Mg in the crystal
2+By 4 O and 2 F coordinations; The solid-solid phase-change temperature is 900 ± 10 ℃, and low temperature has frequency-doubled effect mutually, allows the ultraviolet band light beam to see through; High temperature phase frequency-doubled effect is zero; Decomposition temperature is 1050 ℃; Deliquescence not in air; Be insoluble to the aqueous solution of pH value 2-12 under the normal temperature.
2. by the described barium fluoborate magnesium of claim 1 non-linear optic crystal, it is characterized in that said ultraviolet band light beam is a deep ultraviolet wave band light beam.
3. claim 1 or 2 described barium fluoborate magnesium non-linear optic crystal growth methods, it is a flux growth method, its step is following:
(1) powdery barium fluoborate magnesium and fusing assistant are mixed, be heated to 800-900 ℃, leave standstill or to be stirred to melt even, must contain the mixed melt of barium fluoborate magnesium and fusing assistant;
Said fusing assistant is BaO-LiF-B
2O
3-BF
3System fusing assistant or BaO-NaF-B
2O
3-BF
3The system fusing assistant;
When said fusing assistant is BaO-LiF-B
2O
3-BF
3During the system fusing assistant, the mol ratio of each component is in said barium fluoborate magnesium and the said fusing assistant:
BMBF∶Ba∶B∶F∶Li＝(0.8-1.5)∶(0.12-0.3)∶(0.75-1.2)∶(0.6-1)∶(0-1.5)；
When said fusing assistant is BaO-NaF-B
2O
3-BF
3During the system fusing assistant, the mol ratio of each component is in said barium fluoborate magnesium and the said fusing assistant:
BMBF∶Ba∶B∶F∶Na＝(0.8-1.5)∶(0-0.3)∶(0.6-1.5)∶(0.6-2.7)∶(0.4-1.5)；
(2) through attempting confirming the saturation point temperature of above-mentioned mixed melt, said saturation point temperature is no more than 950 ℃;
The mixed melt temperature is set on the saturation point temperature 0.5-5 ℃, following seed crystal: seed crystal is fixed on the seed rod end, seed crystal is stretched into from the reactors top, make itself and mixed melt surface contact or stretch in the mixed melt; In the time of following seed crystal 0-30 minute, cool the temperature under the saturation point temperature 0-1 ℃, beginning is with 0-40 rev/min of rotating speed rotation seed crystal, and begins cooling with 0.05-5 ℃ of/day rate of temperature fall, and crystal is grown up gradually; When crystal is grown up to desired size, crystal is lifted from mixed melt, with 2-50 ℃ of/hour speed furnace temperature is reduced to room temperature then, obtain barium fluoborate magnesium monocrystalline.
4. by the described barium fluoborate magnesium of claim 3 non-linear optic crystal growth method, it is characterized in that described powdery barium fluoborate magnesium is prepared by the arbitrary reaction formula in the reactions formula:
2BaO+MgF
2+MgO+B
2O
3→2BaMgBO
3F
2MgO+BaF
2+BaO+B
2O
3→2BaMgBO
3F。
5. by the described barium fluoborate magnesium of claim 4 non-linear optic crystal growth method, it is characterized in that the BaO in the described reaction formula is by BaCO
3, Ba (OH)
2Or BaC
2O
4Substitute; MgO is by Mg (CO
3)
4Mg (OH)
25H
2O, Mg (OH)
2Or MgC
2O
4Substitute; B
2O
3By H
3BO
3Substitute.
6. by the described barium fluoborate magnesium of claim 3 non-linear optic crystal growth method, it is characterized in that said powdery barium fluoborate magnesium is substituted by fluorochemicals, boron-containing compound, containing barium compound and the magnesium-containing compound with mol ratio.
7. by the described barium fluoborate magnesium of claim 6 non-linear optic crystal growth method, it is characterized in that said containing
Fluorine cpd are MgF
2, BaF
2, NH
4F or NH
4HF
2
Said boron-containing compound is B
2O
3Or H
3BO
3
Said containing barium compound is BaO, BaCO
3, BaF
2, Ba (OH)
2, BaC
2O
4Or Ba (NO
3)
2
Said magnesium-containing compound is MgO, Mg (CO
3)
4Mg (OH)
25H
2O, MgF
2, Mg (OH)
2, MgC
2O
4Or Mg (NO
3)
2
8. by the described barium fluoborate magnesium of claim 3 non-linear optic crystal growth method, it is characterized in that said BaO-LiF-B
2O
3-BF
3The system fusing assistant is to choose BaCO by identical mol ratio
3, Ba (OH)
2, BaF
2, BaC
2O
4, Ba (NO
3)
2, Li
2CO
3, LiF, B
2O
3, H
3BO
3, NH
4F, NH
4HF
2In three kinds, four kinds or multiple preparation.
9. by the described barium fluoborate magnesium of claim 3 non-linear optic crystal growth method, it is characterized in that said BaO-NaF-B
2O
3-BF
3The system fusing assistant is to choose BaCO by identical mol ratio
3, Ba (OH)
2, BaF
2, BaC
2O
4, Ba (NO
3)
2, Na
2CO
3, NaF, B
2O
3, H
3BO
3, NH
4F, NH
4HF
2In three kinds, four kinds or multiple preparation.
10. the purposes of claim 1 or 2 described barium fluoborate magnesium non-linear optic crystals; It is characterized in that; This barium fluoborate magnesium non-linear optic crystal is used as frequency-doubling crystal in harmonic generator, conversion optical maser wavelength produces the laser of visible light to deep ultraviolet wave band.
11. the purposes of claim 1 or 2 described barium fluoborate magnesium non-linear optic crystals is characterized in that, the laser of 4 frequency multiplication wavelength 266nm of the phase matched output Nd:YAG laser of this barium fluoborate magnesium non-linear optic crystal.
12. the purposes of claim 1 or 2 described barium fluoborate magnesium non-linear optic crystals; It is characterized in that; This barium fluoborate magnesium non-linear optic crystal is used as frequency-doubling crystal in optical parametric oscillator, conversion optical maser wavelength produces the laser of visible light to deep ultraviolet wave band.
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| CN107217301B (en) * | 2016-03-22 | 2019-04-12 | 中国科学院新疆理化技术研究所 | Compound lithium fluoroborate potassium and lithium fluoroborate nonlinear optical crystal of potassium and preparation method and purposes |
| CN106835263B (en) * | 2017-02-20 | 2020-01-03 | 中国科学院新疆理化技术研究所 | Preparation method and application of lithium fluoroborate nonlinear optical crystal |
| CN106868590B (en) * | 2017-02-21 | 2019-02-19 | 中国科学院新疆理化技术研究所 | Compound barium fluoborate magnesium and barium fluoborate magnesium nonlinear optical crystal and preparation method and purposes |
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1146812A (en) * | 1995-02-21 | 1997-04-02 | 克里斯马特克公司 | nonlinear crystal and application thereof |
| US5677921A (en) * | 1995-03-24 | 1997-10-14 | The Regents Of The University Of California | Ytterbium-doped borate fluoride laser crystals and lasers |
| CN1215767A (en) * | 1997-10-28 | 1999-05-05 | 中国科学院福建物质结构研究所 | Non-linear optic crystal aluminium-oxygen-barium borate |
| CN1236027A (en) * | 1998-05-14 | 1999-11-24 | 中国科学技术大学 | Compound R2MB10O10 as non-linear optical crystal and its preparation and use |
-
2009
- 2009-02-11 CN CN200910077443XA patent/CN101798707B/en not_active Expired - Fee Related
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1146812A (en) * | 1995-02-21 | 1997-04-02 | 克里斯马特克公司 | nonlinear crystal and application thereof |
| US5677921A (en) * | 1995-03-24 | 1997-10-14 | The Regents Of The University Of California | Ytterbium-doped borate fluoride laser crystals and lasers |
| CN1215767A (en) * | 1997-10-28 | 1999-05-05 | 中国科学院福建物质结构研究所 | Non-linear optic crystal aluminium-oxygen-barium borate |
| CN1236027A (en) * | 1998-05-14 | 1999-11-24 | 中国科学技术大学 | Compound R2MB10O10 as non-linear optical crystal and its preparation and use |
Non-Patent Citations (2)
| Title |
|---|
| JP特开2002-68891A 2002.03.08 |
| 李如康，陈创天.低温相偏硼酸钡β_BaB_2O_4_晶体倍频系数的计算.《物理学报》.1985,第34卷(第6期), * |
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