CN115198363B - Compound barium lanthanum fluoroborate and barium lanthanum fluoroborate nonlinear optical crystal, preparation method and application - Google Patents
Compound barium lanthanum fluoroborate and barium lanthanum fluoroborate nonlinear optical crystal, preparation method and application Download PDFInfo
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- CN115198363B CN115198363B CN202110375788.4A CN202110375788A CN115198363B CN 115198363 B CN115198363 B CN 115198363B CN 202110375788 A CN202110375788 A CN 202110375788A CN 115198363 B CN115198363 B CN 115198363B
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- 239000013078 crystal Substances 0.000 title claims abstract description 159
- -1 Compound barium lanthanum fluoroborate Chemical class 0.000 title claims abstract description 52
- 230000003287 optical effect Effects 0.000 title claims abstract description 37
- 238000002360 preparation method Methods 0.000 title abstract description 8
- 238000000034 method Methods 0.000 claims abstract description 16
- 239000000126 substance Substances 0.000 claims abstract description 10
- 229910016036 BaF 2 Inorganic materials 0.000 claims description 70
- 238000001816 cooling Methods 0.000 claims description 52
- 150000001875 compounds Chemical class 0.000 claims description 45
- QVQLCTNNEUAWMS-UHFFFAOYSA-N barium oxide Chemical compound [Ba]=O QVQLCTNNEUAWMS-UHFFFAOYSA-N 0.000 claims description 33
- 239000003795 chemical substances by application Substances 0.000 claims description 26
- 239000007788 liquid Substances 0.000 claims description 22
- 239000002994 raw material Substances 0.000 claims description 22
- 239000000203 mixture Substances 0.000 claims description 19
- 229910052788 barium Inorganic materials 0.000 claims description 18
- 229910052746 lanthanum Inorganic materials 0.000 claims description 18
- MRELNEQAGSRDBK-UHFFFAOYSA-N lanthanum(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[La+3].[La+3] MRELNEQAGSRDBK-UHFFFAOYSA-N 0.000 claims description 18
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 claims description 17
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 claims description 17
- 150000003839 salts Chemical class 0.000 claims description 17
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 claims description 16
- 239000004327 boric acid Substances 0.000 claims description 16
- 238000010438 heat treatment Methods 0.000 claims description 15
- 238000002156 mixing Methods 0.000 claims description 15
- 239000011259 mixed solution Substances 0.000 claims description 12
- 238000005303 weighing Methods 0.000 claims description 10
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims description 9
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 claims description 9
- OYLGJCQECKOTOL-UHFFFAOYSA-L barium fluoride Chemical compound [F-].[F-].[Ba+2] OYLGJCQECKOTOL-UHFFFAOYSA-L 0.000 claims description 9
- 229910001632 barium fluoride Inorganic materials 0.000 claims description 9
- 229910052796 boron Inorganic materials 0.000 claims description 9
- 229910052731 fluorine Inorganic materials 0.000 claims description 9
- 239000011737 fluorine Substances 0.000 claims description 9
- IQONKZQQCCPWMS-UHFFFAOYSA-N barium lanthanum Chemical compound [Ba].[La] IQONKZQQCCPWMS-UHFFFAOYSA-N 0.000 claims description 8
- 238000000227 grinding Methods 0.000 claims description 8
- 238000001354 calcination Methods 0.000 claims description 2
- 238000010532 solid phase synthesis reaction Methods 0.000 claims description 2
- 239000011734 sodium Substances 0.000 claims 17
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 claims 8
- HTUMBQDCCIXGCV-UHFFFAOYSA-N lead oxide Chemical compound [O-2].[Pb+2] HTUMBQDCCIXGCV-UHFFFAOYSA-N 0.000 claims 8
- 229910000464 lead oxide Inorganic materials 0.000 claims 5
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims 4
- 239000002131 composite material Substances 0.000 claims 2
- 230000004907 flux Effects 0.000 claims 1
- 229910003002 lithium salt Inorganic materials 0.000 claims 1
- 159000000002 lithium salts Chemical class 0.000 claims 1
- XAEFZNCEHLXOMS-UHFFFAOYSA-M potassium benzoate Chemical compound [K+].[O-]C(=O)C1=CC=CC=C1 XAEFZNCEHLXOMS-UHFFFAOYSA-M 0.000 claims 1
- 159000000000 sodium salts Chemical class 0.000 claims 1
- BYMUNNMMXKDFEZ-UHFFFAOYSA-K trifluorolanthanum Chemical compound F[La](F)F BYMUNNMMXKDFEZ-UHFFFAOYSA-K 0.000 claims 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims 1
- 239000000843 powder Substances 0.000 abstract description 6
- 230000000694 effects Effects 0.000 abstract description 4
- 238000003746 solid phase reaction Methods 0.000 abstract description 4
- 238000006243 chemical reaction Methods 0.000 description 19
- IWOUKMZUPDVPGQ-UHFFFAOYSA-N barium nitrate Chemical compound [Ba+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O IWOUKMZUPDVPGQ-UHFFFAOYSA-N 0.000 description 16
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 description 16
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 16
- 238000003786 synthesis reaction Methods 0.000 description 11
- RQPZNWPYLFFXCP-UHFFFAOYSA-L barium dihydroxide Chemical compound [OH-].[OH-].[Ba+2] RQPZNWPYLFFXCP-UHFFFAOYSA-L 0.000 description 10
- 229910001863 barium hydroxide Inorganic materials 0.000 description 10
- 230000015572 biosynthetic process Effects 0.000 description 10
- 229910017569 La2(CO3)3 Inorganic materials 0.000 description 8
- AYJRCSIUFZENHW-UHFFFAOYSA-L barium carbonate Chemical compound [Ba+2].[O-]C([O-])=O AYJRCSIUFZENHW-UHFFFAOYSA-L 0.000 description 8
- GXUARMXARIJAFV-UHFFFAOYSA-L barium oxalate Chemical compound [Ba+2].[O-]C(=O)C([O-])=O GXUARMXARIJAFV-UHFFFAOYSA-L 0.000 description 8
- 229940094800 barium oxalate Drugs 0.000 description 8
- JKWMSGQKBLHBQQ-UHFFFAOYSA-N diboron trioxide Chemical compound O=BOB=O JKWMSGQKBLHBQQ-UHFFFAOYSA-N 0.000 description 8
- NZPIUJUFIFZSPW-UHFFFAOYSA-H lanthanum carbonate Chemical compound [La+3].[La+3].[O-]C([O-])=O.[O-]C([O-])=O.[O-]C([O-])=O NZPIUJUFIFZSPW-UHFFFAOYSA-H 0.000 description 8
- 229960001633 lanthanum carbonate Drugs 0.000 description 8
- OXHNIMPTBAKYRS-UHFFFAOYSA-H lanthanum(3+);oxalate Chemical compound [La+3].[La+3].[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O OXHNIMPTBAKYRS-UHFFFAOYSA-H 0.000 description 8
- YXEUGTSPQFTXTR-UHFFFAOYSA-K lanthanum(3+);trihydroxide Chemical compound [OH-].[OH-].[OH-].[La+3] YXEUGTSPQFTXTR-UHFFFAOYSA-K 0.000 description 8
- FYDKNKUEBJQCCN-UHFFFAOYSA-N lanthanum(3+);trinitrate Chemical compound [La+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O FYDKNKUEBJQCCN-UHFFFAOYSA-N 0.000 description 8
- VQEHIYWBGOJJDM-UHFFFAOYSA-H lanthanum(3+);trisulfate Chemical compound [La+3].[La+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O VQEHIYWBGOJJDM-UHFFFAOYSA-H 0.000 description 8
- ICAKDTKJOYSXGC-UHFFFAOYSA-K lanthanum(iii) chloride Chemical compound Cl[La](Cl)Cl ICAKDTKJOYSXGC-UHFFFAOYSA-K 0.000 description 8
- 229910052697 platinum Inorganic materials 0.000 description 8
- 229910013184 LiBO Inorganic materials 0.000 description 7
- 238000002844 melting Methods 0.000 description 7
- 230000008018 melting Effects 0.000 description 7
- 229910021193 La 2 O 3 Inorganic materials 0.000 description 6
- 229910052810 boron oxide Inorganic materials 0.000 description 6
- 239000003054 catalyst Substances 0.000 description 6
- 238000005516 engineering process Methods 0.000 description 6
- 239000012856 weighed raw material Substances 0.000 description 6
- 229910017855 NH 4 F Inorganic materials 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 239000004570 mortar (masonry) Substances 0.000 description 4
- BTBUEUYNUDRHOZ-UHFFFAOYSA-N Borate Chemical compound [O-]B([O-])[O-] BTBUEUYNUDRHOZ-UHFFFAOYSA-N 0.000 description 3
- 229910020640 KF—NaF Inorganic materials 0.000 description 3
- 238000002441 X-ray diffraction Methods 0.000 description 3
- 230000005540 biological transmission Effects 0.000 description 3
- 239000012071 phase Substances 0.000 description 3
- 229910011255 B2O3 Inorganic materials 0.000 description 2
- 229910002422 La(NO3)3·6H2O Inorganic materials 0.000 description 2
- 229910052593 corundum Inorganic materials 0.000 description 2
- 239000010431 corundum Substances 0.000 description 2
- 229910052761 rare earth metal Inorganic materials 0.000 description 2
- 229910002651 NO3 Inorganic materials 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 238000013467 fragmentation Methods 0.000 description 1
- 238000006062 fragmentation reaction Methods 0.000 description 1
- 238000001459 lithography Methods 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 239000008204 material by function Substances 0.000 description 1
- 238000005459 micromachining Methods 0.000 description 1
- 230000005693 optoelectronics Effects 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C30—CRYSTAL GROWTH
- C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
- C30B29/00—Single crystals or homogeneous polycrystalline material with defined structure characterised by the material or by their shape
- C30B29/10—Inorganic compounds or compositions
- C30B29/16—Oxides
- C30B29/22—Complex oxides
-
- C—CHEMISTRY; METALLURGY
- C30—CRYSTAL GROWTH
- C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
- C30B1/00—Single-crystal growth directly from the solid state
- C30B1/10—Single-crystal growth directly from the solid state by solid state reactions or multi-phase diffusion
-
- C—CHEMISTRY; METALLURGY
- C30—CRYSTAL GROWTH
- C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
- C30B15/00—Single-crystal growth by pulling from a melt, e.g. Czochralski method
-
- C—CHEMISTRY; METALLURGY
- C30—CRYSTAL GROWTH
- C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
- C30B9/00—Single-crystal growth from melt solutions using molten solvents
- C30B9/04—Single-crystal growth from melt solutions using molten solvents by cooling of the solution
- C30B9/08—Single-crystal growth from melt solutions using molten solvents by cooling of the solution using other solvents
- C30B9/12—Salt solvents, e.g. flux growth
-
- G—PHYSICS
- G02—OPTICS
- G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
- G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
- G02F1/35—Non-linear optics
- G02F1/355—Non-linear optics characterised by the materials used
- G02F1/3551—Crystals
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- Chemical & Material Sciences (AREA)
- Crystallography & Structural Chemistry (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Physics & Mathematics (AREA)
- Nonlinear Science (AREA)
- Inorganic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Physics & Mathematics (AREA)
- Optics & Photonics (AREA)
- Crystals, And After-Treatments Of Crystals (AREA)
Abstract
The invention relates to a preparation method and application of a compound barium lanthanum fluoroborate and a nonlinear optical crystal of barium lanthanum fluoroborate, wherein the chemical formulas of the compound barium lanthanum fluoroborate and the nonlinear optical crystal are Ba 3 La 4 B 3 O 13 F, the crystals belong to a hexagonal system, the space groups are P63 (173), and the unit cell parameters areThe molecular weight is 1227.018, the powder frequency doubling effect is about 6 times KDP (KH 2 PO 4 ). The compound barium lanthanum fluoroborate is synthesized by adopting a solid-phase reaction method, the nonlinear optical crystal of the barium lanthanum fluoroborate is grown by adopting a high-temperature melt method or a pulling method, the preparation method of the crystal is simple, the cost is low, the mechanical hardness of the prepared crystal is high, and the barium lanthanum fluoroborate crystal obtained by the method is applied as a nonlinear optical frequency doubling device.
Description
Technical Field
The invention relates to a chemical formula of Ba 3 La 4 B 3 O 13 F, barium lanthanum fluoroborate and barium lanthanum fluoroborate nonlinear optical crystals, preparation methods of the compounds and the crystals, and frequency conversion devices manufactured by using the crystals.
Background
Nonlinear optical crystals are one of important photoelectric information functional materials and are an important material basis for optoelectronic technology, particularly laser technology. The nonlinear optical crystal material can be used for converting laser frequency and expanding laser wavelength, and is used for adjusting the intensity and phase of laser so as to realize holographic storage of laser signals. Therefore, the nonlinear optical crystal is an indispensable key material in the advanced technology and the modern military technology, and the information technology is put in a development priority position in each country and is brought into advanced technology development planning as an important strategic measure for high importance and support.
The requirements for the second-order nonlinear optical crystal mainly comprise a non-central symmetrical structure, proper double refractive index, wide transmission range in the ultraviolet region, high laser damage threshold, excellent physical and chemical properties and the like. Borate crystals have important application values in the fields of semiconductor lithography, laser micromachining and photochemical synthesis, and the performances of the borate crystals are widely focused. The band gap is larger, the laser damage threshold is higher, the physical and chemical properties are stable, the ultraviolet nonlinear optical crystal is an ideal choice of a novel ultraviolet nonlinear optical crystal, alkaline earth cations and rare earth elements (Ba and La) are introduced into borate, electron transition of d-d and f-f is avoided, and the ultraviolet nonlinear optical crystal is an ideal choice of ultraviolet region transmission. F incorporating large electronegativity - Can widen the transmission range, blue shift the cut-off edge to ultraviolet or even deep ultraviolet region, such as KBE 2 BO 3 F 2 (KBBF). Thus, F is contained in - The synthesis of alkaline earth rare earth borate is an effective means for designing large frequency multiplication effect and being applied to ultraviolet and deep ultraviolet nonlinear optical materials.
Disclosure of Invention
The invention aims to provide a compound lanthanum barium fluoroborate and a barium lanthanum fluoroborate nonlinear optical crystal, the chemical formulas of which are Ba 3 La 4 B 3 O 13 F。
The invention also aims at providing a preparation method for synthesizing the compound barium lanthanum fluoroborate by adopting a solid-phase reaction method and growing the nonlinear optical crystal of the barium lanthanum fluoroborate by adopting a high-temperature melt method or a Czochralski method.
It is a further object of the present invention to provide the use of barium lanthanum fluoroborate nonlinear optical devices for the preparation of frequency doubling generators, up or down frequency converters or optical parametric oscillators.
The technical scheme of the invention is as follows:
the invention provides a compound barium lanthanum fluoroborate, which has a chemical formula of Ba 3 La 4 B 3 O 13 F, preparing the compound Ba by adopting a general chemical synthesis method 3 La 4 B 3 O 13 F, preferentially adopting a solid phase reaction method to lead the element barium in the barium-containing compound to be,The raw materials of lanthanum in the lanthanum-containing compound, boron in the boron-containing compound and fluorine in the fluorine-containing compound with the molar ratio of 2.8-3.2:3.8-4.2:2.8-3.3:0.7-1.2 are uniformly mixed and heated for solid phase reaction, and the chemical formula Ba can be obtained 3 La 4 B 3 O 13 A compound of F.
The following are typical of the Ba obtainable 3 La 4 B 3 O 13 Chemical reaction of F:
1)5BaCO 3 +6H 3 BO 3 +1BaF 2 +4La 2 O 3 →2Ba 3 La 4 B3O 13 F+5CO 2 ↑+9H 2 O↑
2)3BaCO 3 +3H 3 BO 3 +2La 2 O 3 +1NH 4 F→Ba 3 La 4 B 3 O 13 F+1NH 3 ↑+3CO 2 ↑+5H 2 O↑
3)5Ba(OH) 2 +1BaF 2 +6H 3 BO 3 +4La 2 O 3 →2Ba 3 La 4 B 3 O 13 F+14H 2 O↑
4)3BaO+3H 3 BO 3 +2La 2 O 3 +1NH 4 F→Ba 3 La 4 B3O 13 F+5H 2 O↑+NH 3 ↑
5)3Ba(OH) 2 +1NH 4 F+3H 3 BO 3 +2La 2 O 3 →Ba 3 La 4 B 3 O 13 F+8H 2 O↑+1NH3↑
6)5BaO+6H 3 BO 3 +4La 2 O 3 +1BaF 2 →2Ba 3 La 4 B 3 O 13 F+9H 2 O↑
7)5BaCO 3 +6H 3 BO 3 +1BaF 2 +8La(NO 3 ) 3 ·6H 2 O→2Ba 3 La 4 B 3 O 13 F+24NO 2 ↑+57H 2 O↑+5CO 2 ↑+6O 2 ↑
8)3BaCO 3 +3H 3 BO 3 +4La(NO 3 ) 3 ·6H 2 O+1NH 4 F→Ba 3 La 4 B 3 O 13 F+1NH 3 ↑+3CO 2 ↑+12NO 2 ↑+29H 2 O↑+3O 2 ↑
9)1Ba(OH) 2 +2BaCO 3 +1NH 4 F+2La 2 O 3 +3H 3 BO 3 →Ba 3 La 4 B 3 O 13 F+1NH 3 ↑+6H 2 O↑+2CO 2 ↑
10)2Ba(OH) 2 +1BaCO 3 +1NH 4 F+2La 2 O 3 +3H 3 BO 3 →Ba 3 La 4 B 3 O 13 F+1NH 3 ↑+7H 2 O↑+1CO 2 ↑
11)1Ba(OH) 2 +2BaCO 3 +1NH 4 F+4La(NO3) 3 ·6H 2 O+3H 3 BO 3 →Ba 3 La 4 B 3 O 13 F+1NH 3 ↑+30H 2 O↑+2CO 2 ↑+15O 2 ↑
12)2Ba(OH) 2 +1BaCO 3 +1NH 4 F+4La(NO 3 ) 3 ·6H 2 O+3H 3 BO 3 →Ba 3 La 4 B 3 O 13 F+1NH 3 ↑+31H 2 O↑+1CO 2 ↑+15O 2 ↑
13)10BaSO 4 +12H 3 BO 3 +2BaF 2 +8La 2 O 3 →4Ba 3 La 4 B 3 O 13 F+10SO 2 ↑+18H 2 O↑+5O 2 ↑
14)6BaSO 4 +6H 3 BO 3 +4La 2 O 3 +2NH 4 F→2Ba 3 La 4 B 3 O 13 F+2NH 3 ↑+6SO 2 ↑+10H 2 O↑+3O 2 ↑
15)5BaNO 3 +6H 3 BO 3 +1BaF 2 +4La 2 O 3 →2Ba 3 La 4 B3O 13 F+5CO 2 ↑+9H 2 O↑
16)3BaNO 3 +3H 3 BO 3 +2La 2 O 3 +1NH 4 F→Ba 3 La 4 B 3 O 13 F+1NH 3 ↑+3NO 2 ↑+5H 2 O↑
17)1Ba(OH) 2 +2BaNO 3 +1NH 4 F+2La 2 O 3 +3H 3 BO 3 →Ba 3 La 4 B 3 O 13 F+1NH 3 ↑+6H 2 O↑+2NO 2 ↑
18)2Ba(OH) 2 +1BaNO 3 +1NH 4 F+2La 2 O 3 +3H 3 BO 3 →Ba 3 La 4 B 3 O 13 F+1NH 3 ↑+7H 2 O↑+1NO 2 ↑
the invention provides a barium lanthanum fluoroborate nonlinear optical crystal, which is characterized in that the chemical formula of the crystal is Ba 3 La 4 B 3 O 13 F, molecular weight 1227.018, no symmetry center, hexagonal system, space group P63 (173), compound Ba 3 La 4 B 3 O 13 F unit cell parameters areThe powder frequency doubling effect is about 6 times KDP (KH) 2 PO 4 )。
The preparation method of the barium lanthanum fluoroborate nonlinear optical crystal is characterized in that a high-temperature melt method or a pulling method is adopted to grow the compound barium lanthanum fluoroborate nonlinear optical crystal, and the specific operation is as follows:
a. uniformly mixing the compound barium lanthanum fluoroborate and the fluxing agent, heating the mixture to the temperature of 650-1000 ℃ at the heating rate of 1-30 ℃/h, keeping the temperature for 5-80 hours to obtain mixed melt, and cooling the mixed melt to the temperature of 500-800 ℃, wherein the molar ratio of the compound barium lanthanum fluoroborate to the fluxing agent is 1:0.5-25;
or directly weighing raw materials for preparing the compound barium lanthanum fluoroborate or directly weighing a mixture of the raw materials for preparing the compound barium lanthanum fluoroborate and the fluxing agent according to the molar ratio, heating the mixture to the temperature of 650-1000 ℃ at the heating rate of 1-30 ℃/h, keeping the temperature for 5-80 hours to obtain mixed solution, and cooling the mixed solution to the temperature of 500-800 ℃, wherein the molar ratio of the barium-containing compound, the lanthanum-containing compound, the boron-containing compound and the fluorine-containing compound to the fluxing agent is 2.8-3.2:3.8-4.2:2.8-3.3:0.7-1.2:0.1-30;
the fluxing agent being essentially a single fluxing agent, e.g. BaCO 3 、BaF 2 、BaO、H 3 BO 3 、PbO、NaF、Na 2 CO 3 、LiF、Li 2 CO 3 、KF、K 2 CO 3 、LiBO 2 Etc. and other complex fluxing agents, such as BaCO 3 -BaF 2 、BaCO 3 -BaO、BaCO 3 -H 3 BO 3 、BaCO 3 -NaF、BaCO 3 -KF、BaCO 3 -PbO、BaCO 3 -LiF、BaF 2 -BaO、BaF 2 -PbO、BaF 2 -NaF、BaF 2 -Na 2 CO 3 、BaF 2 -LiF、BaF 2 -KF、BaF 2 -K 2 CO 3 、BaO-H 3 BO 3 、BaO-PbO、BaO-NaF、BaO-Na 2 CO 3 、BaO-LiF、BaO-Li 2 CO 3 、BaO-KF、BaO-K 2 CO 3 、BaO-LiBO 2 、H 3 BO 3 -PbO、H 3 BO 3 -Na 2 CO 3 、H 3 BO 3 -Li 2 CO 3 、H 3 BO 3 -KF、H 3 BO 3 -K 2 CO 3 、H 3 BO 3 -LiBO 2 、BaCO 3 -NaF-H 3 BO 3 、BaCO 3 -BaO-H 3 BO 3 、BaCO 3 -LiF-H 3 BO 3 、BaCO 3 -KF-H 3 BO 3 、BaF 2 -BaO-H 3 BO 3 、BaF 2 -NaF-H 3 BO 3 、BaF 2 -LiF-H 3 BO 3 、BaO-BaF 2 -H 3 BO 3 、BaO-NaF-H 3 BO 3 、H 3 BO 3 -PbO-BaF 2 、NaF-PbO-H 3 BO 3 、KF-PbO-H 3 BO 3 、Li 2 CO 3 -PbO-H 3 BO 3 、LiBO 2 -PbO-H 3 BO 3 、H 3 BO 3 -KF-NaF、H 3 BO 3 -K 2 CO 3 -Na 2 CO 3 、H 3 BO 3 -K 2 CO 3 -NaF、H 3 BO 3 -KF-Na 2 CO 3 、H 3 BO 3 -KF-Na 2 CO 3 -BaF 2 、H 3 BO 3 -K 2 CO 3 -NaF-BaF 2 、H 3 BO 3 -PbO-NaF-BaF 2 、H 3 BO 3 -LiF-NaF-BaF 2 、H 3 BO 3 -K 2 CO 3 -LiF-BaF 2 Etc.
The compound barium lanthanum fluoroborate is prepared by adopting a solid-phase synthesis method, and comprises the following steps of: the molar ratio of elemental barium in the barium-containing compound, elemental lanthanum in the lanthanum-containing compound, elemental boron in the boron-containing compound and elemental fluorine in the fluorine-containing compound is 2.8-3.2:3.8-4.2:2.8-3.3:0.7-1.2, the raw materials of the barium-containing compound, the lanthanum-containing compound, the boron-containing compound and the fluorine-containing compound are uniformly mixed, the mixture is put into a muffle furnace after grinding, the mixture is presintered to remove moisture and gas in the raw materials, cooled to room temperature, taken out and ground, then put into the muffle furnace for calcination, the temperature is raised to 600-1300 ℃, the constant temperature is kept for 72 hours, cooled to the room temperature, and the ground mixture is taken out to obtain the compound barium lanthanum fluoroborate.
b. Preparing seed crystals of barium lanthanum fluoborate nonlinear optical crystals: slowly cooling the mixed solution obtained in the step a to room temperature at a speed of 3-10 ℃/h, and spontaneously crystallizing to obtain seed crystals of barium lanthanum fluoroborate nonlinear optical crystals;
c. c, placing the crucible containing the mixed solution prepared in the step a into a crystal growth furnace, fixing the seed crystal obtained in the step b on a seed rod, preheating the seed crystal for 5-60 minutes from the top of the crystal growth furnace, lowering the seed crystal to be in contact with the liquid surface of the mixed solution or the mixed solution for remelting, keeping the temperature for 5-60 minutes, and reducing the temperature to a saturation temperature at a speed of 1-60 ℃/h;
d. and then slowly cooling at the speed of 0.1-5 ℃/day, rotating the seed rod at the speed of 0-60rpm to perform crystal growth, lifting the crystal off the surface of the mixed molten liquid after the single crystal grows to a required size, cooling to room temperature at the speed of 1-80 ℃/h, and taking the crystal out of a hearth to obtain the barium lanthanum fluoborate nonlinear optical crystal.
The fluxing agent BaCO 3 -BaF 2 BaCO in the system 3 With BaF 2 The molar ratio of (2) is 1-3:2-5; baCO 3 BaCO in BaO System 3 The molar ratio of the catalyst to BaO is 1-3:3-6; baCO 3 -H 3 BO 3 BaCO in the system 3 And H is 3 BO 3 The molar ratio is 1-5:3-7; baCO 3 BaCO in NaF System 3 The molar ratio of the catalyst to NaF is 1-5:2-8; baCO 3 BaCO in-KF System 3 The molar ratio of KF to KF is 1-8:2-5; baCO 3 BaCO in PbO systems 3 The mol ratio of the catalyst to PbO is 1-10:3-6; baCO 3 BaCO in LiF System 3 The molar ratio of LiF to LiF is 1-7:1-6; baF (Baf) 2 BaF in PbO System 2 The mol ratio of the catalyst to PbO is 1-7:1-6; baF (Baf) 2 BaF in NaF System 2 The molar ratio of the catalyst to NaF is 1-8:2-5; baF (Baf) 2 -Na 2 CO 3 BaF in System 2 With Na and Na 2 CO 3 The molar ratio is 1-10:3-6; baF (Baf) 2 BaF in LiF System 2 The molar ratio of LiF to LiF is 1-7:5-6; h 3 BO 3 H in PbO System 3 BO 3 The mol ratio of the catalyst to PbO is 1-7:2-6; h 3 BO 3 -Na 2 CO 3 H in the system 3 BO 3 With Na and Na 2 CO 3 The molar ratio is 1-6:1-5; h 3 BO 3 -Li 2 CO 3 H in the system 3 BO 3 With Li 2 CO 3 The molar ratio is 1-6:2-6; h 3 BO 3 H in-KF System 3 BO 3 The molar ratio of KF to KF is 1-6:4-6; h 3 BO 3 -K 2 CO 3 H in the system 3 BO 3 And K is equal to 2 CO 3 The molar ratio is 1-6:2-6; h 3 BO 3 -LiBO 2 H in the system 3 BO 3 And LiBO 2 The molar ratio is 1-5:4-6；BaO-Na 2 CO 3 BaO and Na in the system 2 CO 3 The molar ratio is 1-4:2-6; na in BaO-KF system 2 CO 3 With Na and Na 2 CO 3 The molar ratio is 1-6:1-5; baCO 3 -NaF-H 3 BO 3 BaCO in the system 3 NaF and H 3 BO 3 The molar ratio is 1-5:2-6:3-8; baCO 3 -BaO-H 3 BO 3 BaCO in the system 3 BaO and H 3 BO 3 The molar ratio is 0.5-5:1-6:3-8; baCO 3 -LiF-H 3 BO 3 BaCO in the system 3 LiF and H 3 BO 3 The molar ratio is 1-5:0.5-6:2.9-8; baF (Baf) 2 -LiF-H 3 BO 3 BaF in System 2 LiF and H 3 BO 3 The molar ratio is 1-6:1-7:3-8; baO-BaF 2 -H 3 BO 3 BaO and BaF in the system 2 And H is 3 BO 3 The molar ratio is 1-3:1-4:3-10; baO-NaF-H 3 BO 3 BaO, naF and H in the system 3 BO 3 The molar ratio is 1-5:1-9:3-12; h 3 BO 3 -PbO-BaF 2 H in the system 3 BO 3 PbO and BaF 2 The molar ratio is 2-5:1-6:3-8; naF-PbO-H 3 BO 3 NaF, pbO and H in the system 3 BO 3 The molar ratio is 2-9:1-7:1-10; KF-PbO-H 3 BO 3 KF, pbO and H in the system 3 BO 3 The molar ratio is 2-5:1-6:2-8; li (Li) 2 CO 3 -PbO-H 3 BO 3 Li in the system 2 CO 3 PbO and H 3 BO 3 The molar ratio is 2-5:1-10:2-11; liBO 2 -PbO-H 3 BO 3 LiBO in System 2 PbO and H 3 BO 3 The molar ratio is 0.5-5:1.5-10:2-10; h 3 BO 3 H in-KF-NaF system 3 BO 3 The molar ratio of KF to NaF is 2-5:1-10:2-9; h 3 BO 3 -KF-Na 2 CO 3 -BaF 2 H in the system 3 BO 3 、KF、Na 2 CO 3 With BaF 2 The molar ratio is 1-21:1-10:2-8:1-8; h 3 BO 3 -K 2 CO 3 -NaF-BaF 2 H in the system 3 BO 3 、K 2 CO 3 NaF and BaF 2 The molar ratio is 1-21:1-10:2-8:1-8; h 3 BO 3 -PbO-NaF-BaF 2 H in the system 3 BO 3 、K 2 CO 3 NaF and BaF 2 The molar ratio is 1-20:1-10:2-8:1-8; h 3 BO 3 -LiF-NaF-BaF 2 H in the system 3 BO 3 、K 2 CO 3 NaF and BaF 2 The molar ratio is 1-21:1-10:3-8:1-8; h 3 BO 3 -K 2 CO 3 -LiF-BaF 2 H in the system 3 BO 3 、K 2 CO 3 NaF and BaF 2 The molar ratio is 1-21:2-10:2-9:1-7; h 3 BO 3 -KF-NaF-BaF 2 H in the system 3 BO 3 KF, naF and BaF 2 The molar ratio is 1-18:1-9:2-10:1-9.
The invention provides a barium lanthanum fluoborate nonlinear optical crystal, which is characterized in that the chemical formula of the crystal is Ba 3 La 4 B 3 O 13 F, molecular weight 1227.018, no symmetry center, hexagonal system, space group P63 (173), compound Ba 3 La 4 B 3 O 13 F unit cell parameters areThe powder frequency doubling effect is about 6 times KDP (KH) 2 PO 4 ). The grown barium lanthanum fluoroborate nonlinear optical crystal has the advantages of high purity, large crystal size, transparency, no package, high growth speed, low cost, easy obtainment of crystals with large size, wide light-transmitting wave band, high hardness, good mechanical property, difficult fragmentation and deliquescence, easy processing and storage and the like. The barium lanthanum fluoroborate nonlinear optical crystal is used for preparing a frequency multiplication conversion generator, an upper frequency converter, a lower frequency converter or an optical parametric oscillator. YAG Q-switched laser is used as light source at room temperature, infrared light with incident wavelength of 1064nm is used as light source, green laser with wavelength of 532nm is output, and the laser intensity is equal to KDP (KH 2 PO 4 ) Is 6 times as large as that of the above.
Drawings
FIG. 1 shows Ba of the invention 3 La 4 B 3 O 13 X-ray diffraction pattern of the F powder.
FIG. 2 shows Ba of the invention 3 La 4 B 3 O 13 Working principle diagram of nonlinear optical device made of F crystal, wherein 1 is laser, 2 is emitted light beam, 3 is Ba 3 La 4 B 3 O 13 And F, the crystal, 4 is an emergent light beam, and 5 is a filter.
Detailed Description
The invention is described in detail below with reference to the attached drawings and examples:
example 1:
according to the reaction formula: 5BaCO 3 +6H 3 BO 3 +2BaF 2 +4La 2 O 3 →2Ba 3 La 4 B 3 O 13 F+2CO 2 ↑+9H 2 Synthesis of Ba by O ≡ 3 La 4 B 3 O 13 Compound F:
BaCO is carried out 3 、H 3 BO 3 、BaF 2 、La 2 O 3 Weighing according to a molar ratio of 5:6:2:4, placing into a mortar, mixing, grinding, then placing into an open corundum crucible with phi of 100mm multiplied by 100mm, placing into a muffle furnace, slowly heating to 300 ℃, keeping the temperature for 24 hours, cooling to room temperature, taking out, grinding for the second time, placing into the muffle furnace, heating to 950 ℃, keeping the temperature for 24 hours, cooling to room temperature, taking out, grinding for the third time, placing into the muffle furnace, keeping the temperature for 48 hours at 950 ℃, taking out, grinding to obtain barium lanthanum fluoroborate single-phase polycrystalline powder, and carrying out X-ray analysis on the product to obtain an X-ray spectrogram and barium lanthanum fluoroborate Ba 3 La 4 B 3 O 13 The X-ray spectrogram obtained by the F single crystal structure is consistent;
the obtained barium lanthanum fluoborate Ba 3 La 4 B 3 O 13 F compound single-phase polycrystalline powder and fluxing agent H 3 BO 3 KF-NaF is calculated according to the mole ratio Ba 3 La 4 B 3 O 13 F:H 3 BO 3 -KF-naf=1:3, wherein H 3 BO 3 Mixing KF and NaF in the molar ratio of 6:3:5, loading into an open platinum crucible with phi 80mm multiplied by 80mm, heating to 900 ℃ at the temperature rising rate of 30 ℃/h, keeping the temperature for 15 hours to obtain mixed melt, and cooling to 880 ℃;
slowly cooling to room temperature at the speed of 0.5 ℃/h, and spontaneously crystallizing to obtain barium lanthanum fluoroborate seed crystal;
growing crystals in a compound melt: ba to be obtained 3 La 4 B 3 O 13 F, fixing the seed crystal on a seed rod from the top of a crystal growth furnace to the seed crystal, preheating the seed crystal on the surface of the mixed melt for 10 minutes, immersing the seed crystal in the liquid level, carrying out back melting on the seed crystal in the mixed melt, keeping the temperature for 30 minutes, and rapidly cooling to the saturation temperature of 865 ℃;
then cooling at a rate of 2 ℃/day, rotating the seed rod at a rotation speed of 10rpm, separating the crystal from the liquid surface after the crystal growth is completed, and cooling to room temperature at a rate of 10 ℃/hour to obtain Ba with a size of 56mm×40mm×30mm 3 La 4 B 3 O 13 And F, crystal.
The raw material barium carbonate in the reaction formula can be replaced by other barium-containing salts such as barium fluoride, barium nitrate, barium oxalate, barium sulfate and the like, barium oxide or barium hydroxide, lanthanum oxide can be replaced by other lanthanum-containing salts such as lanthanum carbonate, lanthanum nitrate, lanthanum chloride, lanthanum oxalate, lanthanum sulfate and the like, lanthanum hydroxide, and boric acid can be replaced by boron oxide.
Example 2:
according to the reaction formula: 3BaCO 3 +3H 3 BO 3 +2La 2 O 3 +1NH 4 F→Ba 3 La 4 B 3 O 13 F+NH3↑+4NO 2 ↑+3CO 2 ↑+5H 2 Synthesis of Ba by O ≡ 3 La 4 B 3 O 13 Compound F:
BaCO is carried out 3 、H 3 BO 3 、La 2 O 3 、NH 4 F, directly weighing raw materials according to a molar ratio of 3:3:2:1, and mixing the weighed raw materials with a fluxing agent H 3 BO 3 PbO is mixed according to a mol ratio of 1:4, wherein H is as follows 3 BO 3 Molar with PbOPlacing the mixture into an open platinum crucible with the diameter of 80mm multiplied by 80mm according to the ratio of 3:5, heating to 870 ℃, keeping the temperature for 60 hours to obtain mixed melt, and cooling to 850 ℃;
slowly cooling to room temperature at a speed of 1.5 ℃/h, and spontaneously crystallizing to obtain barium lanthanum fluoroborate seed crystal;
will obtain Ba 3 La 4 B 3 O 13 F, fixing the seed crystal on a seed rod from the top of a crystal growth furnace to the seed crystal, preheating the seed crystal on the surface of the mixed melt for 10 minutes, immersing the seed crystal under the liquid level, carrying out back melting on the seed crystal in the mixed melt, keeping the temperature for 30 minutes, and rapidly cooling to the saturation temperature of 820 ℃;
slowly cooling at a rate of 1 ℃/day without rotating the seed rod, lifting the crystal from the surface of the molten liquid after the crystal grows to a required size, cooling to room temperature at a rate of 20 ℃/h, and taking the crystal out of the hearth to obtain the Ba with a size of 36mm multiplied by 22mm multiplied by 15mm 3 La 4 B 3 O 13 And F, crystal.
The raw material barium carbonate in the reaction formula can be replaced by other barium-containing salts such as barium fluoride, barium nitrate, barium oxalate, barium sulfate and the like, barium oxide or barium hydroxide, lanthanum oxide can be replaced by other lanthanum-containing salts such as lanthanum carbonate, lanthanum nitrate, lanthanum chloride, lanthanum oxalate, lanthanum sulfate and the like, lanthanum hydroxide, and boric acid can be replaced by boron oxide.
Example 3:
according to the reaction formula: 5Ba (OH) 2 +1BaF 2 +6H 3 BO 3 +4La 2 O 3 →2Ba 3 La 4 B 3 O 13 F+14H 2 Synthesis of Ba by O ≡ 3 La 4 B 3 O 13 Compound F:
ba (OH) 2 、BaF 2 、H 3 BO 3 、La 2 O 3 Directly weighing raw materials according to a molar ratio of 5:1:6:4, and mixing the weighed raw materials with a fluxing agent BaF 2 -H 3 BO 3 Mixing according to a molar ratio of 1:3, wherein BaF 2 And H is 3 BO 3 The mixture is put into an open platinum crucible with the mol ratio of 1:3 and phi 80mm multiplied by 80mm, and is heated to the temperature of 900 ℃ and is kept at constant temperature60 hours to obtain mixed melt, and then cooling to 880 ℃;
slowly cooling to room temperature at the speed of 3.5 ℃/h, and spontaneously crystallizing to obtain barium lanthanum fluoroborate seed crystal;
ba to be obtained 3 La 4 B 3 O 13 F, fixing the seed crystal on a seed rod from the top of a crystal growth furnace to the seed crystal, preheating the seed crystal on the surface of the mixed melt for 15 minutes, immersing the seed crystal under the liquid level, carrying out back melting on the seed crystal in the mixed melt, keeping the temperature for 30 minutes, and rapidly cooling to the saturation temperature of 867 ℃;
slowly cooling at 3 deg.C/day, rotating the seed crystal crucible at 5rpm, lifting the crystal from the surface of molten liquid after the crystal grows to the required size, cooling to room temperature at 1 deg.C/h, and taking out the crystal from the hearth to obtain Ba with the size of 25mm×24mm×10mm 3 La 4 B 3 O 13 And F, crystal.
The raw material barium hydroxide in the reaction formula can be replaced by other barium-containing salts such as barium fluoride, barium nitrate, barium oxalate, barium sulfate and the like, barium oxide or barium hydroxide, lanthanum oxide can be replaced by other lanthanum-containing salts such as lanthanum carbonate, lanthanum nitrate, lanthanum chloride, lanthanum oxalate, lanthanum sulfate and the like, lanthanum hydroxide, and boric acid can be replaced by boron oxide.
Example 4:
according to the reaction formula: 3BaO+3H 3 BO 3 +2La 2 O 3 +1NH 4 F↑→Ba 3 La 4 B 3 O 13 F+5H 2 O↑+NH 3 Synthesis of Ba by ≡ 3 La 4 B 3 O 13 Compound F:
BaO, H 3 BO 3 、La 2 O 3 、NH 4 F, directly weighing raw materials according to a molar ratio of 3:3:2:1, and mixing the weighed raw materials with a fluxing agent PbO-H 3 BO 3 Mixing according to a molar ratio of 1:3, wherein PbO and H 3 BO 3 Placing the mixture into an open platinum crucible with the mol ratio of phi 80mm multiplied by 80mm, heating to the temperature of 890 ℃, keeping the temperature for 80 hours to obtain mixed melt, and then cooling to the temperature of 875 ℃;
slowly cooling to room temperature at a speed of 5 ℃/h, and spontaneously crystallizing to obtain barium lanthanum fluoroborate seed crystal;
ba to be obtained 3 La 4 B 3 O 13 F, fixing the seed crystal on a seed rod from the top of a crystal growth furnace to the seed crystal, preheating the seed crystal on the surface of the mixed melt for 20 minutes, immersing the seed crystal under the liquid level, carrying out back melting on the seed crystal in the mixed melt, keeping the temperature for 5 minutes, and rapidly cooling to the saturation temperature of 860 ℃;
then slowly cooling at a speed of 3 ℃/day, rotating a seed rod at a speed of 15rpm, separating the crystal from the surface of the molten liquid after the crystal grows to a required size, cooling to room temperature at a speed of 15 ℃/h, and taking out the crystal from a hearth to obtain Ba with a size of 35mm multiplied by 25mm multiplied by 20mm 3 La 4 B 3 O 13 And F, crystal.
The raw material barium oxide in the reaction formula can be replaced by other barium-containing salts such as barium fluoride, barium nitrate, barium oxalate, barium sulfate and the like, or barium oxide or barium hydroxide, lanthanum oxide can be replaced by other lanthanum-containing salts such as lanthanum carbonate, lanthanum nitrate, lanthanum chloride, lanthanum oxalate, lanthanum sulfate and the like, or lanthanum hydroxide, and boric acid can be replaced by boric oxide.
Example 5
According to the reaction formula: 3Ba (OH) 2 +1NH 4 F+3H 3 BO 3 +2La 2 O 3 →Ba 3 La 4 B 3 O 13 F+8H 2 Synthesis of Ba by O ≡ +1NH3 ≡ 3 La 4 B 3 O 13 Compound F:
ba (OH) 2 、NH 4 F、H 3 BO 3 、La 2 O 3 Directly weighing raw materials according to a molar ratio of 3:1:3:2, and mixing the weighed raw materials with a fluxing agent H 3 BO 3 -KF-Na 2 CO 3 Mixing according to a molar ratio of 1:2, wherein H 3 BO 3 KF and Na 2 CO 3 Placing the mixture into an open platinum crucible with the diameter of 80mm multiplied by 80mm according to the molar ratio of 5:1:3, heating to the temperature of 850 ℃, keeping the temperature for 80 hours to obtain mixed melt, and then cooling to the temperature of 830 ℃;
slowly cooling to room temperature at a speed of 10 ℃/h, and spontaneously crystallizing to obtain barium lanthanum fluoroborate seed crystal;
ba to be obtained 3 La 4 B 3 O 13 F, fixing the seed crystal on a seed rod from the top of a crystal growth furnace to the seed crystal, preheating the seed crystal on the surface of the mixed melt for 25 minutes, partially immersing the seed crystal under the liquid surface, carrying out back melting on the seed crystal in the mixed melt, keeping the temperature for 25 minutes, and rapidly cooling to the saturation temperature of 820 ℃;
then cooling at a speed of 5 ℃/day, rotating the seed rod at a speed of 30rpm, lifting the crystal from the surface of the molten liquid after the crystal grows to a required size, cooling to room temperature at a speed of 35 ℃/h, and taking the crystal out of the hearth to obtain the Ba with a size of 22mm multiplied by 32mm multiplied by 20mm 3 La 4 B 3 O 13 And F, crystal.
The raw material barium hydroxide in the reaction formula can be replaced by other barium-containing salts such as barium fluoride, barium nitrate, barium oxalate, barium sulfate and the like, barium oxide or barium hydroxide, lanthanum oxide can be replaced by other lanthanum-containing salts such as lanthanum carbonate, lanthanum nitrate, lanthanum chloride, lanthanum oxalate, lanthanum sulfate and the like, lanthanum hydroxide, and boric acid can be replaced by boron oxide.
Example 6
According to the reaction formula: 5BaO+6H 3 BO 3 +4La 2 O 3 +1BaF 2 →2Ba 3 La 4 B 3 O 13 F+9H 2 Synthesis of Ba by O ≡ 3 La 4 B 3 O 13 Compound F:
BaO, H 3 BO 3 、La 2 O 3 、BaF 2 Directly weighing raw materials according to a molar ratio of 5:6:4:1, and mixing the weighed raw materials with a fluxing agent H 3 BO 3 -KF is compounded in a molar ratio of 1:4, wherein H 3 BO 3 The mixture is put into an open platinum crucible with phi 80mm multiplied by 80mm, the temperature is increased to 900 ℃ and kept constant for 5 hours to obtain mixed melt, and then the mixed melt is reduced to 880 ℃;
slowly cooling to room temperature at the speed of 4.0 ℃/h, and spontaneously crystallizing to obtain barium lanthanum fluoroborate seed crystal;
ba to be obtained 3 La 4 B 3 O 13 F seed crystal is fixed on seed rodPreheating seed crystals on the surface of the mixed molten liquid for 20 minutes, immersing the seed crystals under the liquid surface, carrying out remelting on the seed crystals in the mixed molten liquid, keeping the temperature for 25 minutes, and rapidly cooling to the saturation temperature of 865 ℃;
then cooling at a speed of 3 ℃/day, rotating a seed rod at a speed of 50rpm, separating the crystal from the surface of the molten liquid after the crystal grows to a required size, cooling to room temperature at a speed of 70 ℃/h, and taking the crystal out of a hearth to obtain the Ba with a size of 22mm multiplied by 21mm multiplied by 16mm 3 La 4 B 3 O 13 And F, crystal.
The raw material barium oxide in the reaction formula can be replaced by other barium-containing salts such as barium fluoride, barium nitrate, barium oxalate, barium sulfate and the like, or barium oxide or barium hydroxide, lanthanum oxide can be replaced by other lanthanum-containing salts such as lanthanum carbonate, lanthanum nitrate, lanthanum chloride, lanthanum oxalate, lanthanum sulfate and the like, or lanthanum hydroxide, and boric acid can be replaced by boric oxide.
Example 7
According to the reaction formula: 5BaCO 3 +6H 3 BO 3 +1BaF 2 +8La(NO 3 ) 3 ·6H 2 O→2Ba 3 La 4 B 3 O 13 F+24NO 2 ↑+57H 2 O↑+5CO 2 ↑+6O 2 Synthesis of Ba by ≡ 3 La 4 B 3 O 13 Compound F:
BaCO is carried out 3 、H 3 BO 3 、BaF 2 、La(NO 3 ) 3 ·6H 2 O is put into a mortar according to the mol ratio of 5:6:1:8, mixed and finely ground, then is put into an open corundum crucible with phi of 100mm multiplied by 100mm, is tightly pressed, is put into a muffle furnace, is slowly heated to the temperature of 400 ℃ and is kept at the constant temperature for 4 hours, is taken out of the crucible after cooling, is loose at the moment, is taken out of the crucible, is uniformly ground again, is put into the crucible again, is taken out in the muffle furnace, is kept at the temperature of 950 ℃ for 48 hours again, is taken out, is put into the mortar, and is smashed and ground to obtain Ba 3 La 4 B 3 O 13 F compound, performing X-ray analysis on the product to obtain X-ray spectrogram and barium lanthanum fluoborate Ba 3 La 4 B 3 O 13 The X-ray spectrogram obtained by the F single crystal structure is consistent;
to be synthesized of Ba 3 La 4 B 3 O 13 F Compound and fluxing agent H 3 BO 3 -PbO-BaF 2 Mixing according to a molar ratio of 1:4, wherein H 3 BO 3 PbO and BaF 2 The molar ratio is 5:1:1, the mixture is put into an open platinum crucible with phi 80mm multiplied by 80mm, the temperature is raised to 900 ℃, the mixture is kept at the constant temperature for 50 hours to obtain mixed melt, and then the mixture is lowered to 880 ℃;
slowly cooling to room temperature at the speed of 4.0 ℃/h, and spontaneously crystallizing to obtain barium lanthanum fluoroborate seed crystal;
ba to be obtained 3 La 4 B 3 O 13 F, fixing the seed crystal on a seed rod from the top of a crystal growth furnace to the seed crystal, preheating the seed crystal on the surface of the mixed melt for 20 minutes, immersing the seed crystal under the liquid level, carrying out back melting on the seed crystal in the mixed melt, keeping the temperature for 25 minutes, and cooling to the saturation temperature of 850 ℃;
then cooling at a speed of 2 ℃/day, rotating the seed rod at a speed of 28rpm, separating the crystal from the surface of the molten liquid after the crystal grows to a required size, cooling to room temperature at a speed of 25 ℃/h, and taking out the crystal from a hearth to obtain Ba with a size of 30mm multiplied by 22mm multiplied by 15mm 3 La 4 B 3 O 13 And F, crystal.
The raw material barium carbonate in the reaction formula can be replaced by other barium-containing salts such as barium fluoride, barium nitrate, barium oxalate, barium sulfate and the like, barium oxide or barium hydroxide, lanthanum oxide can be replaced by other lanthanum-containing salts such as lanthanum carbonate, lanthanum nitrate, lanthanum chloride, lanthanum oxalate, lanthanum sulfate and the like, lanthanum hydroxide, and boric acid can be replaced by boron oxide.
Example 8
According to the reaction formula: 3BaCO 3 +3H 3 BO 3 +4La(NO 3 ) 3 ·6H 2 O+1NH 4 F→Ba 3 La 4 B 3 O 13 F+1NH 3 ↑+3CO 2 ↑+12NO 2 ↑+29H 2 O↑+3O 2 Synthesis of Ba by ≡ 3 La 4 B 3 O 13 Compound F:
BaCO is carried out 3 、H 3 BO 3 、La(NO 3 ) 3 ·6H 2 O、NH 4 F、O 2 Putting the weighed raw materials and a fluxing agent H into a mortar according to a molar ratio of 3:3:4:1:21 3 BO 3 -PbO-NaF-BaF 2 Mixing according to a molar ratio of 1:1, wherein H 3 BO 3 PbO, naF and BaF 2 The molar ratio is 5:3:4:1, the mixture is put into an open platinum crucible with phi of 80mm multiplied by 80mm, the temperature is raised to 890 ℃, the temperature is kept for 80 hours, mixed melt is obtained, and then the temperature is lowered to 865 ℃;
slowly cooling to room temperature at a speed of 10 ℃/h, and spontaneously crystallizing to obtain barium lanthanum fluoroborate seed crystal;
ba to be obtained 3 La 4 B 3 O 13 F, fixing the seed crystal on a seed rod from the top of a crystal growth furnace to the seed crystal, preheating the seed crystal on the surface of the mixed melt for 25 minutes, partially immersing the seed crystal under the liquid surface, carrying out back melting on the seed crystal in the mixed melt, keeping the temperature for 25 minutes, and rapidly cooling to the saturation temperature of 840 ℃;
then cooling at a speed of 5 ℃/day, rotating the seed rod at a speed of 30rpm, lifting the crystal from the surface of the molten liquid after the crystal grows to a required size, cooling to room temperature at a speed of 35 ℃/h, and taking the crystal out of the hearth to obtain the Ba with a size of 22mm multiplied by 32mm multiplied by 20mm 3 La 4 B 3 O 13 And F, crystal.
The raw material barium carbonate in the reaction formula can be replaced by other barium-containing salts such as barium fluoride, barium nitrate, barium oxalate, barium sulfate and the like, barium oxide or barium hydroxide, lanthanum oxide can be replaced by other lanthanum-containing salts such as lanthanum carbonate, lanthanum nitrate, lanthanum chloride, lanthanum oxalate, lanthanum sulfate and the like, lanthanum hydroxide, and boric acid can be replaced by boron oxide.
Example 9
Any of the Ba obtained in examples 1-8 3 La 4 B 3 O 13 F crystal is processed into a frequency doubling device with the size of 5mm multiplied by 6mm according to the matching direction, and is arranged at the position of 3 according to the figure 2, at room temperature, a tone QNd which is YAG laser is used as a light source, the incident wavelength is 1064nm, and the tone QNd which is YAG laser 1 emits light with the wavelength ofAn infrared beam 2 of 1064nm enters Ba 3 La 4 B 3 O 13 F single crystal 3, producing green frequency multiplication light with 532nm wavelength, outputting intensity 6 times of that of KDP with same condition, emitting light beam 4 containing 1064nm infrared light and 532nm green light, filtering by filter 5 to obtain 532nm green laser.
Claims (5)
1. A barium lanthanum fluoborate nonlinear optical crystal is characterized in that the chemical formula is Ba 3 La 4 B 3 O 13 F, the crystal belongs to a hexagonal system, and the space groups are all P6 3 The unit cell parameters areThe molecular weight is 1227.018.
2. The method for preparing the barium lanthanum fluoroborate nonlinear optical crystal according to claim 1, wherein the specific operation is carried out according to the following steps:
a. uniformly mixing the compound barium lanthanum fluoroborate and the fluxing agent, heating the mixture to the temperature of 650-1000 ℃ at the heating rate of 1-30 ℃/h, keeping the temperature for 5-80 hours to obtain mixed melt, and cooling the mixed melt to the temperature of 500-800 ℃, wherein the molar ratio of the compound barium lanthanum fluoroborate to the fluxing agent is 1:0.5-25;
or directly weighing raw materials for preparing the compound barium lanthanum fluoroborate or directly weighing a mixture of the raw materials for preparing the compound barium lanthanum fluoroborate and the fluxing agent according to the molar ratio, heating the mixture to the temperature of 650-1000 ℃ at the heating rate of 1-30 ℃/h, keeping the temperature for 5-80 hours to obtain mixed solution, and cooling the mixed solution to the temperature of 500-800 ℃, wherein the molar ratio of the barium-containing compound, the lanthanum-containing compound, the boron-containing compound and the fluorine-containing compound to the fluxing agent is 2.8-3.2:3.8-4.2:2.8-3.3:0.7-1.2:0.1-30;
the compound barium lanthanum fluoroborate is prepared by adopting a solid-phase synthesis method, and comprises the following steps of: uniformly mixing raw materials of the barium-containing compound, the lanthanum-containing compound, the boron-containing compound and the fluorine-containing compound in a molar ratio of 2.8-3.2:3.8-4.2:2.8-3.3:0.7-1.2, grinding, placing the mixture into a muffle furnace, presintering to remove water and gas in the raw materials, cooling to room temperature, taking out, grinding, placing into the muffle furnace for calcination, heating to 600-1300 ℃, keeping the temperature for 72 hours, cooling to room temperature, taking out, and grinding to obtain the compound barium lanthanum fluoroborate;
b. preparing seed crystals of barium lanthanum fluoborate nonlinear optical crystals: slowly cooling the mixed solution obtained in the step a to room temperature at a speed of 3-10 ℃/h, and spontaneously crystallizing to obtain seed crystals of barium lanthanum fluoroborate nonlinear optical crystals;
c. c, placing the crucible containing the mixed solution prepared in the step a into a crystal growth furnace, fixing the seed crystal obtained in the step b on a seed rod, preheating the seed crystal for 5-60 minutes from the top of the crystal growth furnace, lowering the seed crystal to be in contact with the liquid surface of the mixed solution or the mixed solution for remelting, keeping the temperature for 5-60 minutes, and reducing the temperature to a saturation temperature at a speed of 1-60 ℃/h;
d. and then slowly cooling at the speed of 0.1-5 ℃/day, rotating the seed rod at the speed of 0-60rpm to perform crystal growth, lifting the crystal off the surface of the mixed molten liquid after the single crystal grows to a required size, cooling to room temperature at the speed of 1-80 ℃/h, and taking the crystal out of a hearth to obtain the barium lanthanum fluoborate nonlinear optical crystal.
3. The method of claim 2 wherein the molar ratio of the barium lanthanum fluoroborate compound to the flux is from 1:1 to 20; or wherein the molar ratio of the barium-containing compound, the lanthanum-containing compound, the boron-containing compound, and the fluorine-containing compound to the fluxing agent is 2.8-3.2:3.8-4.2:2.8-3.3:0.7-1.2:1-20; the fluxing agent is single fluxing agent or composite fluxing agent, the single fluxing agent is one or more of barium oxide, lanthanum oxide, boric acid, barium fluoride, lanthanum fluoride, lead oxide, sodium salt, potassium salt and lithium salt, and the composite fluxing agent is BaF 2 -H 3 BO 3 、NaF-H 3 BO 3 、LiF-H 3 BO 3 、Na 2 CO 3 -H 3 BO 3 、Li 2 CO 3 -H 3 BO 3 、K 2 CO 3 -H 3 BO 3 、BaF 2 -PbO、NaF-PbO、LiF-PbO、Na 2 CO 3 -PbO、Li 2 CO 3 -PbO、K 2 CO 3 -PbO、PbO-H 3 BO 3 、BaF 2 -H 3 BO 3 -PbO、NaF-H 3 BO 3 -PbO、LiF-H 3 BO 3 -PbO、Na 2 CO 3 -H 3 BO 3 -PbO、Li 2 CO 3 -H 3 BO 3 -PbO、K 2 CO 3 -H 3 BO 3 -PbO、LiF-BaF 2 -H 3 BO 3 、NaF-BaF 2 -H 3 BO 3 、NaF-LiF-H 3 BO 3 、LiF-Na 2 CO 3 -H 3 BO 3 、LiF-K 2 CO 3 -H 3 BO 3 、NaF-Na 2 CO 3 -H 3 BO 3 、NaF-K 2 CO 3 -H 3 BO 3 、KF-Na 2 CO 3 -H 3 BO 3 -BaF 2 、KF-H 3 BO 3 -PbO、KF-Na 2 CO 3 -H 3 BO 3 、KF-K 2 CO 3 -H 3 BO 3 、KF-BaF 2 -K 2 CO 3 -H 3 BO 3 、NaF-Na 2 CO 3 -H 3 BO 3 、NaF-BaF 2 -Na 2 CO 3 -H 3 BO 3 、NaF-LiF-H 3 BO 3 -BaF 2 、KF-LiF-H 3 BO 3 -BaF 2 、PbO-H 3 BO 3 -BaF 2 、K 2 CO 3 -PbO-BaF 2 、NaF-PbO-BaF 2 、NaF-H 3 BO 3 -BaF 2 、NaF-H 3 BO 3 -BaF 2 、LiF-H 3 BO 3 -BaF 2 、LiF-Na 2 CO 3 -H 3 BO 3 -BaF 2 One or more of the following.
4. A method according to claim 3, characterized in that the BaF 2 -H 3 BO 3 、PbO-H 3 BO 3 、NaF-H 3 BO 3 Or LiF-H 3 BO 3 The molar ratio of the fluoride to the boric acid is 0.1-10:0.2-20; the Na is 2 CO 3 -H 3 BO 3 、Li 2 CO 3 -H 3 BO 3 Or K 2 CO 3 -H 3 BO 3 The molar ratio of the carbonate to the boric acid is 0.2-15:0.1-30; the BaF 2 -the molar ratio of fluoride to lead oxide in PbO, liF-PbO is 0.5-19:0.5-26; the Na is 2 CO 3 -PbO、Li 2 CO 3 -PbO、K 2 CO 3 The molar ratio of carbonate to lead oxide in PbO is 0.2-15:1-19; the KF-H 3 BO 3 -PbO、BaF 2 -H 3 BO 3 -PbO、NaF-H 3 BO 3 -PbO、LiF-H 3 BO 3 The molar ratio of fluoride, boric acid and lead oxide in PbO is 0.1-10:0.2-13:1-21; the Na is 2 CO 3 -H 3 BO 3 -PbO、Li 2 CO 3 -H 3 BO 3 -PbO、K 2 CO 3 -H 3 BO 3 -PbO carbonate, boric acid and lead oxide in a molar ratio of 1-13:0.5-19:0.4-26; the NaF-BaF 2 -H 3 BO 3 、NaF-LiF-H 3 BO 3 、LiF-BaF 2 -H 3 BO 3 The molar ratio of the first fluoride, the second fluoride and the boric acid is 0.1-21:1-16:0.7-20; the LiF-Na 2 CO 3 -H 3 BO 3 、LiF-K 2 CO 3 -H 3 BO 3 、NaF-Na 2 CO 3 -H 3 BO 3 、NaF-K 2 CO 3 -H 3 BO 3 、KF-Na 2 CO 3 -H 3 BO 3 、KF-K 2 CO 3 -H 3 BO 3 The molar ratio of the fluoride, the carbonate and the boric acid is 1-10:0.5-14:1-20; the KF-BaF 2 -Na 2 CO 3 -H 3 BO 3 、KF-BaF 2 -K 2 CO 3 -H 3 BO 3 First fluoride, second fluoride, carbonic acidThe molar ratio of the salt to the boric acid is 0.1-23:1-17:0.7-23:1-24.
5. Use of the barium lanthanum fluoroborate nonlinear optical crystal according to claim 1, wherein the barium lanthanum fluoroborate nonlinear optical crystal is used for preparing a frequency multiplier converter.
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| CN102978702A (en) * | 2011-09-02 | 2013-03-20 | 中国科学院新疆理化技术研究所 | Compound barium borofluoride, barium borofluoride non-linear optical crystal, and preparation method and use of the barium borofluoride non-linear optical crystal |
| CN106868590A (en) * | 2017-02-21 | 2017-06-20 | 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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| CN102978702A (en) * | 2011-09-02 | 2013-03-20 | 中国科学院新疆理化技术研究所 | Compound barium borofluoride, barium borofluoride non-linear optical crystal, and preparation method and use of the barium borofluoride non-linear optical crystal |
| CN106868590A (en) * | 2017-02-21 | 2017-06-20 | 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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