CN115198363A - Compound barium lanthanum fluoborate, barium lanthanum fluoborate nonlinear optical crystal, preparation method and application - Google Patents
Compound barium lanthanum fluoborate, barium lanthanum fluoborate nonlinear optical crystal, preparation method and application Download PDFInfo
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- CN115198363A CN115198363A CN202110375788.4A CN202110375788A CN115198363A CN 115198363 A CN115198363 A CN 115198363A CN 202110375788 A CN202110375788 A CN 202110375788A CN 115198363 A CN115198363 A CN 115198363A
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- 239000013078 crystal Substances 0.000 title claims abstract description 167
- 150000001875 compounds Chemical class 0.000 title claims abstract description 74
- IQONKZQQCCPWMS-UHFFFAOYSA-N barium lanthanum Chemical compound [Ba].[La] IQONKZQQCCPWMS-UHFFFAOYSA-N 0.000 title claims abstract description 57
- 230000003287 optical effect Effects 0.000 title claims abstract description 38
- 238000002360 preparation method Methods 0.000 title abstract description 7
- 238000000034 method Methods 0.000 claims abstract description 24
- 239000000126 substance Substances 0.000 claims abstract description 11
- 238000003746 solid phase reaction Methods 0.000 claims abstract description 5
- 229910016036 BaF 2 Inorganic materials 0.000 claims description 71
- 238000001816 cooling Methods 0.000 claims description 36
- QVQLCTNNEUAWMS-UHFFFAOYSA-N barium oxide Chemical compound [Ba]=O QVQLCTNNEUAWMS-UHFFFAOYSA-N 0.000 claims description 35
- 229910052746 lanthanum Inorganic materials 0.000 claims description 20
- 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 20
- 229910052788 barium Inorganic materials 0.000 claims description 19
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 claims description 19
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 claims description 18
- IWOUKMZUPDVPGQ-UHFFFAOYSA-N barium nitrate Chemical compound [Ba+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O IWOUKMZUPDVPGQ-UHFFFAOYSA-N 0.000 claims description 18
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 claims description 18
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 claims description 18
- 239000004327 boric acid Substances 0.000 claims description 17
- 239000002994 raw material Substances 0.000 claims description 17
- 238000002156 mixing Methods 0.000 claims description 16
- 239000003795 chemical substances by application Substances 0.000 claims description 14
- RQPZNWPYLFFXCP-UHFFFAOYSA-L barium dihydroxide Chemical compound [OH-].[OH-].[Ba+2] RQPZNWPYLFFXCP-UHFFFAOYSA-L 0.000 claims description 11
- OYLGJCQECKOTOL-UHFFFAOYSA-L barium fluoride Chemical compound [F-].[F-].[Ba+2] OYLGJCQECKOTOL-UHFFFAOYSA-L 0.000 claims description 11
- 229910001632 barium fluoride Inorganic materials 0.000 claims description 11
- 229910001863 barium hydroxide Inorganic materials 0.000 claims description 11
- 230000004907 flux Effects 0.000 claims description 11
- 239000007788 liquid Substances 0.000 claims description 11
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims description 10
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 claims description 10
- 229910052796 boron Inorganic materials 0.000 claims description 10
- 229910052731 fluorine Inorganic materials 0.000 claims description 10
- 239000011737 fluorine Substances 0.000 claims description 10
- 238000005303 weighing Methods 0.000 claims description 10
- 229910017569 La2(CO3)3 Inorganic materials 0.000 claims description 9
- GXUARMXARIJAFV-UHFFFAOYSA-L barium oxalate Chemical compound [Ba+2].[O-]C(=O)C([O-])=O GXUARMXARIJAFV-UHFFFAOYSA-L 0.000 claims description 9
- 229940094800 barium oxalate Drugs 0.000 claims description 9
- 229910052810 boron oxide Inorganic materials 0.000 claims description 9
- JKWMSGQKBLHBQQ-UHFFFAOYSA-N diboron trioxide Chemical compound O=BOB=O JKWMSGQKBLHBQQ-UHFFFAOYSA-N 0.000 claims description 9
- 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 claims description 9
- 229960001633 lanthanum carbonate Drugs 0.000 claims description 9
- 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 claims description 9
- YXEUGTSPQFTXTR-UHFFFAOYSA-K lanthanum(3+);trihydroxide Chemical compound [OH-].[OH-].[OH-].[La+3] YXEUGTSPQFTXTR-UHFFFAOYSA-K 0.000 claims description 9
- 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 claims description 9
- 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 claims description 9
- 239000000203 mixture Substances 0.000 claims description 8
- 238000010438 heat treatment Methods 0.000 claims description 7
- 239000011734 sodium Substances 0.000 claims 19
- HTUMBQDCCIXGCV-UHFFFAOYSA-N lead oxide Chemical compound [O-2].[Pb+2] HTUMBQDCCIXGCV-UHFFFAOYSA-N 0.000 claims 9
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 claims 8
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims 5
- 229910000464 lead oxide Inorganic materials 0.000 claims 5
- BYMUNNMMXKDFEZ-UHFFFAOYSA-K trifluorolanthanum Chemical compound F[La](F)F BYMUNNMMXKDFEZ-UHFFFAOYSA-K 0.000 claims 3
- 159000000009 barium salts Chemical class 0.000 claims 2
- 150000002603 lanthanum Chemical class 0.000 claims 2
- DDFHBQSCUXNBSA-UHFFFAOYSA-N 5-(5-carboxythiophen-2-yl)thiophene-2-carboxylic acid Chemical compound S1C(C(=O)O)=CC=C1C1=CC=C(C(O)=O)S1 DDFHBQSCUXNBSA-UHFFFAOYSA-N 0.000 claims 1
- 229910004261 CaF 2 Inorganic materials 0.000 claims 1
- RDQNDQHTCDIXNE-UHFFFAOYSA-K [La+3].[O-]N=O.[O-]N=O.[O-]N=O Chemical compound [La+3].[O-]N=O.[O-]N=O.[O-]N=O RDQNDQHTCDIXNE-UHFFFAOYSA-K 0.000 claims 1
- ITHZDDVSAWDQPZ-UHFFFAOYSA-L barium acetate Chemical compound [Ba+2].CC([O-])=O.CC([O-])=O ITHZDDVSAWDQPZ-UHFFFAOYSA-L 0.000 claims 1
- GJTDJAPHKDIQIQ-UHFFFAOYSA-L barium(2+);dinitrite Chemical compound [Ba+2].[O-]N=O.[O-]N=O GJTDJAPHKDIQIQ-UHFFFAOYSA-L 0.000 claims 1
- WAKZZMMCDILMEF-UHFFFAOYSA-H barium(2+);diphosphate Chemical compound [Ba+2].[Ba+2].[Ba+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O WAKZZMMCDILMEF-UHFFFAOYSA-H 0.000 claims 1
- AYJRCSIUFZENHW-DEQYMQKBSA-L barium(2+);oxomethanediolate Chemical compound [Ba+2].[O-][14C]([O-])=O AYJRCSIUFZENHW-DEQYMQKBSA-L 0.000 claims 1
- 239000002131 composite material Substances 0.000 claims 1
- LQFNMFDUAPEJRY-UHFFFAOYSA-K lanthanum(3+);phosphate Chemical compound [La+3].[O-]P([O-])([O-])=O LQFNMFDUAPEJRY-UHFFFAOYSA-K 0.000 claims 1
- JLRJWBUSTKIQQH-UHFFFAOYSA-K lanthanum(3+);triacetate Chemical compound [La+3].CC([O-])=O.CC([O-])=O.CC([O-])=O JLRJWBUSTKIQQH-UHFFFAOYSA-K 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
- 230000000694 effects Effects 0.000 abstract description 5
- 239000000843 powder Substances 0.000 abstract description 5
- 238000006243 chemical reaction Methods 0.000 description 19
- 150000003839 salts Chemical class 0.000 description 16
- AYJRCSIUFZENHW-UHFFFAOYSA-L barium carbonate Chemical compound [Ba+2].[O-]C([O-])=O AYJRCSIUFZENHW-UHFFFAOYSA-L 0.000 description 8
- ICAKDTKJOYSXGC-UHFFFAOYSA-K lanthanum(iii) chloride Chemical compound Cl[La](Cl)Cl ICAKDTKJOYSXGC-UHFFFAOYSA-K 0.000 description 8
- 229910013184 LiBO Inorganic materials 0.000 description 7
- 239000011259 mixed solution Substances 0.000 description 7
- 229910021193 La 2 O 3 Inorganic materials 0.000 description 6
- 238000005516 engineering process Methods 0.000 description 6
- 239000000155 melt Substances 0.000 description 6
- 239000000463 material Substances 0.000 description 5
- BTBUEUYNUDRHOZ-UHFFFAOYSA-N Borate Chemical compound [O-]B([O-])[O-] BTBUEUYNUDRHOZ-UHFFFAOYSA-N 0.000 description 4
- 229910020640 KF—NaF Inorganic materials 0.000 description 4
- 229910017855 NH 4 F Inorganic materials 0.000 description 4
- 238000007599 discharging Methods 0.000 description 4
- 238000002844 melting Methods 0.000 description 4
- 230000008018 melting Effects 0.000 description 4
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 4
- 230000005540 biological transmission Effects 0.000 description 3
- 239000004570 mortar (masonry) Substances 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000011068 loading method Methods 0.000 description 2
- 239000012071 phase Substances 0.000 description 2
- 229910052697 platinum Inorganic materials 0.000 description 2
- 229910052761 rare earth metal Inorganic materials 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- 229910002422 La(NO3)3·6H2O Inorganic materials 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- 238000002083 X-ray spectrum Methods 0.000 description 1
- -1 alkaline earth metal cations Chemical class 0.000 description 1
- 150000001342 alkaline earth metals Chemical class 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 230000005274 electronic transitions Effects 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000008204 material by function Substances 0.000 description 1
- 238000005459 micromachining Methods 0.000 description 1
- 238000001259 photo etching Methods 0.000 description 1
- 150000002910 rare earth metals Chemical class 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 238000010532 solid phase synthesis reaction Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
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- 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
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- 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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- Crystals, And After-Treatments Of Crystals (AREA)
Abstract
The invention relates to a compound barium lanthanum fluoborate, a preparation method and application of a barium lanthanum fluoborate nonlinear optical crystal, wherein the chemical formulas of the barium lanthanum fluoborate and the nonlinear optical crystal are Ba 3 La 4 B 3 O 13 F, the crystal belongs to a hexagonal crystal system, the space group is P63 (173), and the unit cell parameter is
The molecular weight is 1227.018, and the powder frequency doubling effect is about 6 times KDP (KH) 2 PO 4 ). The compound barium lanthanum fluoborate is synthesized by a solid-phase reaction method, the barium lanthanum fluoborate nonlinear optical crystal grows by 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 fluoborate 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 fluoborate nonlinear optical crystal, preparation methods of the compound and the crystal, and a frequency conversion device manufactured by using the crystal.
Background
The nonlinear optical crystal is one of important photoelectric information functional materials, and is an important material basis of photoelectron 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 and realizing holographic storage of laser signals. Therefore, the nonlinear optical crystal is an indispensable key material in high and new technology and modern military technology, and information technology is placed in the development priority position of all countries and is incorporated into the development plan of the high and new technology as an important strategic measure which is highly valued and supported.
The requirements for the second-order nonlinear optical crystal mainly include a non-centrosymmetric structure, proper birefringence, wide transmission range in an ultraviolet region, high laser damage threshold, excellent physical and chemical properties and the like. The borate crystal has important application value in the fields of semiconductor photoetching, laser micromachining and photochemical synthesis, and the performance of the borate crystal is concerned widely. The band gap is large, the laser damage threshold is high, the physical and chemical properties are stable, the optical crystal is an ideal selection for novel ultraviolet nonlinear optical crystals, and alkaline earth metal cations and rare earth elements (Ba and La) are introduced into borate, so that electronic transitions of d-d and f-f are avoided, and the optical crystal is an ideal selection for ultraviolet region transmission. F incorporating large electronegativity - Can widen the transmission range, and make the cut-off edge blue shift to ultraviolet or even deep ultraviolet region, such as KBe 2 BO 3 F 2 (KBBF). Thus, containing F - The synthesis of the alkaline earth metal rare earth borate is an effective means for designing large frequency doubling effect and applying the large frequency doubling effect to ultraviolet and deep ultraviolet nonlinear optical materials.
Disclosure of Invention
The invention aims toProvides a compound lanthanum barium fluoborate and a barium lanthanum fluoborate nonlinear optical crystal, the chemical formulas are Ba 3 La 4 B 3 O 13 F。
The invention also aims to provide a method for synthesizing the compound barium lanthanum fluoborate by adopting a solid-phase reaction method and a method for preparing the barium lanthanum fluoborate nonlinear optical crystal by adopting a high-temperature melt method or a pulling method.
It is a further object of the present invention to provide the use of barium lanthanum fluoborate nonlinear optical devices for the preparation of frequency doublers, 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 fluoborate, the chemical formula of which is Ba 3 La 4 B 3 O 13 F, the compound Ba can be prepared by adopting a general chemical synthesis method 3 La 4 B 3 O 13 And F, preferentially adopting a solid-phase reaction method, uniformly mixing raw materials, wherein the molar ratio of the element barium in the barium-containing compound to the element lanthanum in the lanthanum-containing compound to the element boron in the boron-containing compound to the element fluorine in the fluorine-containing compound is 2.8-3.2, and then heating the raw materials to perform solid-phase reaction, so that the raw materials with the chemical formula of Ba 3 La 4 B 3 O 13 A compound of F.
The following are typical of the Ba available 3 La 4 B 3 O 13 F, chemical reaction:
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 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 1227.018Has no symmetry center, belongs to a hexagonal system, has space group of P63 (173), and is a compound Ba 3 La 4 B 3 O 13 The unit cell parameter of F is
The powder has frequency doubling effect of 6 times KDP (KH) 2 PO 4 )。
The preparation method of the barium lanthanum fluoborate nonlinear optical crystal is characterized in that a high-temperature melt method or a pulling method is adopted to grow the compound barium lanthanum fluoborate nonlinear optical crystal, and the specific operation is as follows:
a. uniformly mixing a compound barium lanthanum fluoborate with a 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 a mixed melt, and cooling to the temperature of 500-800 ℃, wherein the molar ratio of the compound barium lanthanum fluoborate to the fluxing agent is 1;
or directly weighing the raw material for preparing the compound barium lanthanum fluoborate according to the molar ratio or directly weighing the mixture of the raw material for preparing the compound barium lanthanum fluoborate and the fluxing agent according to the molar ratio, heating the mixture to 650-1000 ℃ at the heating rate of 1-30 ℃/h, keeping the temperature for 5-80 hours to obtain a mixed melt, and cooling the mixed melt to 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;
the flux consists essentially of a single flux, such as 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 fluxes, e.g. 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 And so on.
The compound barium lanthanum fluoborate is prepared by a solid-phase synthesis method, and comprises the following steps: the molar ratio of the element barium in the barium-containing compound, the element lanthanum in the lanthanum-containing compound, the element boron in the boron-containing compound and the element fluorine in the fluorine-containing compound is 2.8-3.2.
b. Preparing seed crystals of barium lanthanum fluoborate nonlinear optical crystals: b, slowly cooling the mixed solution obtained in the step a to room temperature at the speed of 3-10 ℃/h, and spontaneously crystallizing to obtain the seed crystal of the barium lanthanum fluoborate nonlinear optical crystal;
c. b, 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 crystal rod, placing the seed crystal from the top of the crystal growth furnace, preheating the seed crystal for 5-60 minutes, placing the seed crystal until the seed crystal is in contact with the liquid level of the mixed solution or the mixed solution for remelting, keeping the temperature for 5-60 minutes, and reducing the temperature to the saturation temperature at the rate of 1-60 ℃/h;
d. slowly cooling at the speed of 0.1-5 ℃/day, rotating the seed rod at the rotating speed of 0-60rpm to grow crystals, lifting the crystals away from the surface of the mixed solution after the crystals grow to the required size, cooling to room temperature at the speed of 1-80 ℃/h, and taking out the crystals from the 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 1-3; baCO 3 BaCO in the-BaO system 3 The mol ratio of the compound to BaO is 1-3; baCO 3 -H 3 BO 3 BaCO in the system 3 And H 3 BO 3 The molar ratio is 1-5; baCO 3 BaCO in NaF system 3 The mol ratio of NaF to NaF is 1-5; baCO 3 BaCO in-KF System 3 The molar ratio of the compound to KF is 1-8; baCO 3 BaCO in-PbO system 3 The molar ratio of the compound to PbO is 1-10; baCO 3 BaCO in LiF system 3 The mol ratio of the compound to LiF is 1-7; baF 2 BaF in the-PbO system 2 The molar ratio of the compound to PbO is 1-7; baF 2 BaF in the NaF system 2 The molar ratio of NaF to NaF is 1-8; baF 2 -Na 2 CO 3 In-system BaF 2 With Na 2 CO 3 The mol ratio is 1-10; baF 2 BaF in LiF system 2 The mol ratio of the compound to LiF is 1-7; h 3 BO 3 H in the-PbO System 3 BO 3 The molar ratio of the PbO to the PbO is 1-7; h 3 BO 3 -Na 2 CO 3 In the system H 3 BO 3 With Na 2 CO 3 1-6; h 3 BO 3 -Li 2 CO 3 In the system H 3 BO 3 With Li 2 CO 3 The molar ratio is 1-6; h 3 BO 3 H in-KF system 3 BO 3 The molar ratio of the catalyst to KF is 1-6; h 3 BO 3 -K 2 CO 3 In the system H 3 BO 3 And K 2 CO 3 The molar ratio is 1-6; h 3 BO 3 -LiBO 2 In the system H 3 BO 3 With LiBO 2 The molar ratio is 1-5; baO-Na 2 CO 3 BaO and Na in the system 2 CO 3 The molar ratio is 1-4; na in BaO-KF system 2 CO 3 With Na 2 CO 3 1-5 of molar ratio of 1-6; baCO 3 -NaF-H 3 BO 3 In-system BaCO 3 NaF and H 3 BO 3 The molar ratio is 1-5; baCO 3 -BaO-H 3 BO 3 In-system BaCO 3 BaO and H 3 BO 3 The molar ratio is 0.5-5; baCO 3 -LiF-H 3 BO 3 In-system BaCO 3 LiF and H 3 BO 3 The molar ratio is 1-5; baF 2 -LiF-H 3 BO 3 BaF in the system 2 LiF and H 3 BO 3 1-6; baO-BaF 2 -H 3 BO 3 BaO and BaF in the system 2 And H 3 BO 3 1-3; baO-NaF-H 3 BO 3 BaO, naF and H in the system 3 BO 3 1-5; h 3 BO 3 -PbO-BaF 2 In the system H 3 BO 3 PbO and BaF 2 The molar ratio is 2-5; naF-PbO-H 3 BO 3 NaF, pbO and H in the system 3 BO 3 The molar ratio is 2-9; KF-PbO-H 3 BO 3 KF, pbO and H in the system 3 BO 3 2-5; li 2 CO 3 -PbO-H 3 BO 3 In the system Li 2 CO 3 PbO and H 3 BO 3 The molar ratio is 2-5; liBO 2 -PbO-H 3 BO 3 LiBO in system 2 PbO and H 3 BO 3 The molar ratio is 0.5-5; h 3 BO 3 H in-KF-NaF System 3 BO 3 And the molar ratio of KF to NaF is 2-5; h 3 BO 3 -KF-Na 2 CO 3 -BaF 2 In the system H 3 BO 3 、KF、Na 2 CO 3 With BaF 2 1-21; h 3 BO 3 -K 2 CO 3 -NaF-BaF 2 In the system H 3 BO 3 、K 2 CO 3 NaF and BaF 2 1-21; h 3 BO 3 -PbO-NaF-BaF 2 In the system H 3 BO 3 、K 2 CO 3 NaF and BaF 2 1-20; h 3 BO 3 -LiF-NaF-BaF 2 In the system H 3 BO 3 、K 2 CO 3 NaF and BaF 2 1-21; h 3 BO 3 -K 2 CO 3 -LiF-BaF 2 In the system H 3 BO 3 、K 2 CO 3 NaF and BaF 2 1-21; h 3 BO 3 -KF-NaF-BaF 2 In the system H 3 BO 3 KF, naF and BaF 2 1-18.
The barium lanthanum fluoborate nonlinear optical crystal provided by the invention is characterized in that the chemical formula of the crystal is Ba 3 La 4 B 3 O 13 F, molecular weight of 1227.018, no symmetry center, belonging to hexagonal system, all space groups being P63 (173), compound Ba 3 La 4 B 3 O 13 The unit cell parameter of F is
The powder has frequency doubling effect of about 6 times KDP (KH) 2 PO 4 ). The grown barium lanthanum fluoborate nonlinear optical crystal has high purity, is easy to grow and is transparent without package, and has the advantages of high growth speed, low cost, easy obtaining of crystals with larger size, wider light-transmitting wave band, higher hardness, good mechanical property, difficult cracking and deliquescence, easy processing and storage and the like. The barium lanthanum fluoborate nonlinear optical crystal is used for preparing a frequency doubling conversion generator, an upper frequency converter, a lower frequency converter or an optical parametric oscillator. At room temperature, using Nd-YAG Q-switched laser as light source, inputting 1064nm infrared light, outputting 532nm green laser with intensity equivalent to KDP (KH) 2 PO 4 ) 6 times of the total weight of the product.
Drawings
FIG. 1 shows Ba of the present invention 3 La 4 B 3 O 13 X-ray diffraction pattern of F powder.
FIG. 2 shows Ba of the present 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, and 3 is Ba 3 La 4 B 3 O 13 F crystal, 4 is an emergent light beam, and 5 is a filter plate.
Detailed Description
The invention is described in detail below with reference to the following figures 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 O ↓ [ O ] synthetic Ba 3 La 4 B 3 O 13 A compound F:
mixing BaCO 3 、H 3 BO 3 、BaF 2 、La 2 O 3 Weighing and placing the materials into a mortar according to a molar ratio of 5 3 La 4 B 3 O 13 The X-ray spectrograms obtained from the F single crystal structure are consistent;
the obtained barium lanthanum fluoborate Ba 3 La 4 B 3 O 13 Single-phase polycrystalline powder of compound F and flux H 3 BO 3 -KF-NaF in molar ratio Ba 3 La 4 B 3 O 13 F:H 3 BO 3 -KF-NaF =1, wherein H 3 BO 3 And the molar ratio of KF to NaF is 6;
slowly cooling to room temperature at the speed of 0.5 ℃/h, and spontaneously crystallizing to obtain barium lanthanum fluoborate seed crystals;
growing crystals in a compound melt: ba to be obtained 3 La 4 B 3 O 13 Fixing the seed crystal F on a seed crystal rod, discharging the seed crystal from the top of a crystal growth furnace, preheating the seed crystal on the surface of the mixed melt for 10 minutes, immersing the seed crystal in the liquid level, melting the seed crystal in the mixed melt, keeping the temperature for 30 minutes, and rapidly cooling to the saturation temperature of 865 ℃;
cooling at a rate of 2 ℃/day, rotating the seed rod at a speed of 10rpm, separating the crystal from the liquid surface after the crystal growth is finished, and cooling to room temperature at a rate of 10 ℃/hour to obtain Ba of 56mm × 40mm × 30mm 3 La 4 B 3 O 13 And F, crystals.
The barium carbonate in the reaction formula can be replaced by barium fluoride or barium nitrate or barium oxalate or barium sulfate and other barium-containing salts or barium oxide or barium hydroxide, lanthanum oxide can be replaced by lanthanum carbonate or lanthanum nitrate or lanthanum chloride or lanthanum oxalate or lanthanum sulfate and other lanthanum-containing salts or 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 O ↓ [ O ] synthetic Ba 3 La 4 B 3 O 13 The compound F:
mixing BaCO 3 、H 3 BO 3 、La 2 O 3 、NH 4 F, directly weighing raw materials according to a molar ratio of 3 3 BO 3 -PbO is mixed according to a molar ratio of 1 3 BO 3 The molar ratio of the PbO to the PbO is 3;
slowly cooling to room temperature at the speed of 1.5 ℃/h, and spontaneously crystallizing to obtain barium lanthanum fluoborate seed crystals;
will obtain Ba 3 La 4 B 3 O 13 Fixing the seed crystal F on a seed crystal rod, discharging the seed crystal from the top of a crystal growth furnace, preheating the seed crystal on the surface of the mixed melt for 10 minutes, immersing the seed crystal below the liquid level to melt the seed crystal back in the mixed melt, keeping the temperature for 30 minutes, and quickly cooling to the saturation temperature of 820 ℃;
slowly cooling at a speed of 1 ℃/day, not rotating a seed rod, lifting the crystal away from the surface of the melt after the crystal grows to a required size, cooling to room temperature at a speed of 20 ℃/h, and taking out the crystal from a hearth to obtain Ba with the size of 36mm multiplied by 22mm multiplied by 15mm 3 La 4 B 3 O 13 F, crystals.
The barium carbonate in the reaction formula can be replaced by barium fluoride or barium nitrate or barium oxalate or barium sulfate and other barium-containing salts or barium oxide or barium hydroxide, lanthanum oxide can be replaced by lanthanum carbonate or lanthanum nitrate or lanthanum chloride or lanthanum oxalate or lanthanum sulfate and other lanthanum-containing salts or 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 O ↓ [ O ] synthetic Ba 3 La 4 B 3 O 13 The compound F:
mixing Ba (OH) 2 、BaF 2 、H 3 BO 3 、La 2 O 3 And directly weighing raw materials according to a molar ratio of 5 2 -H 3 BO 3 Mixing according to a molar ratio of 1 2 And H 3 BO 3 Loading the mixture into a platinum crucible with an opening diameter of 80mm multiplied by 80mm and a molar ratio of 1;
slowly cooling to room temperature at the speed of 3.5 ℃/h, and spontaneously crystallizing to obtain barium lanthanum fluoborate seed crystals;
ba to be obtained 3 La 4 B 3 O 13 Fixing the F seed crystal on a seed crystal rod, descending the seed crystal from the top of a crystal growth furnace, preheating the seed crystal on the surface of the mixed melt for 15 minutes, immersing the seed crystal below the liquid level to melt the seed crystal back in the mixed melt, keeping the temperature for 30 minutes, and quickly cooling to the saturation temperature of 867 ℃;
slowly cooling at the speed of 3 ℃/day, rotating the seed crystal crucible at the rotating speed of 5rpm, lifting the crystal away from the surface of the melt after the crystal grows to the required size, cooling to room temperature at the speed of 1 ℃/h, and taking out the crystal from the hearth to obtain Ba with the size of 25mm multiplied by 24mm multiplied by 10mm 3 La 4 B 3 O 13 F, crystals.
The raw material barium hydroxide in the reaction formula can be replaced by barium fluoride or barium nitrate or barium oxalate or barium sulfate and other barium-containing salts or barium oxide or barium hydroxide, lanthanum oxide can be replaced by lanthanum carbonate or lanthanum nitrate or lanthanum chloride or lanthanum oxalate or lanthanum sulfate and other lanthanum-containing salts or 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 ↓ [ O ] synthetic Ba 3 La 4 B 3 O 13 The compound F:
mixing BaO and H 3 BO 3 、La 2 O 3 、NH 4 F, directly weighing raw materials according to a molar ratio of 3 3 BO 3 Mixing the components according to a molar ratio of 1 3 BO 3 The molar ratio is 1;
slowly cooling to room temperature at the speed of 5 ℃/h, and spontaneously crystallizing to obtain barium lanthanum fluoborate seed crystals;
ba to be obtained 3 La 4 B 3 O 13 Fixing the F seed crystal on a seed crystal rod, descending the seed crystal from the top of a crystal growing furnace, preheating the seed crystal on the surface of the mixed solution for 20 minutes, immersing the seed crystal below the liquid level to melt the seed crystal back in the mixed solution, keeping the temperature for 5 minutes, and quickly cooling to the saturation temperature of 860 ℃;
then slowly cooling at the speed of 3 ℃/day, rotating the seed rod at the rotating speed of 15rpm, separating the crystal body from the surface of the melt after the crystal grows to the required size, cooling to room temperature at the speed of 15 ℃/h, and taking out the crystal from the hearth to obtain the Ba with the size of 35mm multiplied by 25mm multiplied by 20mm 3 La 4 B 3 O 13 F, crystals.
In the reaction formula, the raw material barium oxide can be replaced by barium fluoride or barium nitrate or barium oxalate or barium sulfate and other barium-containing salts or barium oxide or barium hydroxide, lanthanum oxide can be replaced by lanthanum carbonate or lanthanum nitrate or lanthanum chloride or lanthanum oxalate or lanthanum sulfate and other lanthanum-containing salts or lanthanum hydroxide, and boric acid can be replaced by boron 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 O ↓ +1NH3 ← synthesized Ba 3 La 4 B 3 O 13 The compound F:
mixing Ba (OH) 2 、NH 4 F、H 3 BO 3 、La 2 O 3 Directly weighing raw materials according to the molar ratio of 3 3 BO 3 -KF-Na 2 CO 3 Mixing according to a molar ratio of 1 3 BO 3 KF and Na 2 CO 3 Loading the mixture into a platinum crucible with an opening diameter of 80mm multiplied by 80mm according to a molar ratio of 5;
slowly cooling to room temperature at the speed of 10 ℃/h, and spontaneously crystallizing to obtain barium lanthanum fluoborate seed crystals;
ba to be obtained 3 La 4 B 3 O 13 Fixing the seed crystal F on a seed crystal rod, descending the seed crystal from the top of a crystal growth furnace, preheating the seed crystal on the surface of the mixed melt for 25 minutes, partially immersing the seed crystal below the liquid level, melting the seed crystal back in the mixed melt, keeping the temperature for 25 minutes, and rapidly cooling to the saturation temperature of 820 ℃;
cooling at the rate of 5 ℃/day, rotating the seed rod at the rotating speed of 30rpm, lifting the crystal away from the surface of the melt after the crystal grows to the required size, cooling to room temperature at the rate of 35 ℃/h, and taking out the crystal from the hearth to obtain Ba with the size of 22mm multiplied by 32mm multiplied by 20mm 3 La 4 B 3 O 13 F, crystals.
The raw material barium hydroxide in the reaction formula can be replaced by barium fluoride or barium nitrate or barium oxalate or barium sulfate and other barium-containing salts or barium oxide or barium hydroxide, lanthanum oxide can be replaced by lanthanum carbonate or lanthanum nitrate or lanthanum chloride or lanthanum oxalate or lanthanum sulfate and other lanthanum-containing salts or 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 O ↓ ] synthetic Ba 3 La 4 B 3 O 13 The compound F:
mixing BaO and H 3 BO 3 、La 2 O 3 、BaF 2 Directly weighing raw materials according to the molar ratio of 5 3 BO 3 -KF is compounded in a molar ratio of 1 3 BO 3 The molar ratio of the raw material to KF is 3;
slowly cooling to room temperature at the speed of 4.0 ℃/h, and spontaneously crystallizing to obtain barium lanthanum fluoborate seed crystals;
ba to be obtained 3 La 4 B 3 O 13 Fixing the seed crystal F on a seed crystal rod, descending the seed crystal from the top of a crystal growth furnace, preheating the seed crystal on the surface of the mixed melt for 20 minutes, immersing the seed crystal below the liquid level to melt the seed crystal back in the mixed melt, keeping the temperature for 25 minutes, and quickly cooling to the saturation temperature of 865 ℃;
then cooling at the speed of 3 ℃/day, rotating the seed rod at the rotating speed of 50rpm, separating the crystal body from the surface of the melt after the crystal grows to the required size, cooling to room temperature at the speed of 70 ℃/h, and taking out the crystal from the hearth to obtain Ba with the size of 22mm multiplied by 21mm multiplied by 16mm 3 La 4 B 3 O 13 F, crystals.
In the reaction formula, the raw material barium oxide can be replaced by barium fluoride or barium nitrate or barium oxalate or barium sulfate and other barium-containing salts or barium oxide or barium hydroxide, lanthanum oxide can be replaced by lanthanum carbonate or lanthanum nitrate or lanthanum chloride or lanthanum oxalate or lanthanum sulfate and other lanthanum-containing salts or lanthanum hydroxide, and boric acid can be replaced by boron 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 ↓ [ O ] synthetic Ba 3 La 4 B 3 O 13 A compound F:
mixing BaCO 3 、H 3 BO 3 、BaF 2 、La(NO 3 ) 3 ·6H 2 Placing O into a mortar according to a molar ratio of 5 3 La 4 B 3 O 13 F compound, X-ray analysis of the product and X-ray spectrum and Ba lanthanum fluoborate 3 La 4 B 3 O 13 The X-ray spectrograms obtained from the F single crystal structures are consistent;
synthesized Ba 3 La 4 B 3 O 13 Compound F and flux H 3 BO 3 -PbO-BaF 2 Mixing according to a molar ratio of 1 3 BO 3 PbO and BaF 2 The molar ratio of 1;
slowly cooling to room temperature at the speed of 4.0 ℃/h, and spontaneously crystallizing to obtain barium lanthanum fluoborate seed crystals;
ba to be obtained 3 La 4 B 3 O 13 Fixing the seed crystal F on a seed crystal rod, discharging the seed crystal from the top of a crystal growing furnace, preheating the seed crystal on the surface of the mixed melt for 20 minutes, immersing the seed crystal below the liquid level, melting the seed crystal back in the mixed melt, keeping the temperature for 25 minutes, and cooling to the saturation temperature of 850 ℃;
then the temperature is reduced at the speed of 2 ℃/day, the seed rod is rotated at the rotating speed of 28rpm, and after the crystal grows to the required size, the crystal body is separated from the solutionCooling the surface to room temperature at a speed of 25 ℃/h, and taking out the crystal from a hearth to obtain Ba with the size of 30mm multiplied by 22mm multiplied by 15mm 3 La 4 B 3 O 13 And F, crystals.
The barium carbonate in the reaction formula can be replaced by barium fluoride or barium nitrate or barium oxalate or barium sulfate and other barium-containing salts or barium oxide or barium hydroxide, lanthanum oxide can be replaced by lanthanum carbonate or lanthanum nitrate or lanthanum chloride or lanthanum oxalate or lanthanum sulfate and other lanthanum-containing salts or 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 ↓ [ O ] synthetic Ba 3 La 4 B 3 O 13 A compound F:
mixing BaCO 3 、H 3 BO 3 、La(NO 3 ) 3 ·6H 2 O、NH 4 F、O 2 Placing the mixture into a mortar according to a molar ratio of 3 3 BO 3 -PbO-NaF-BaF 2 Mixing according to a molar ratio of 1 3 BO 3 PbO, naF and BaF 2 The molar ratio of (5);
slowly cooling to room temperature at the speed of 10 ℃/h, and spontaneously crystallizing to obtain barium lanthanum fluoborate seed crystals;
ba to be obtained 3 La 4 B 3 O 13 Fixing the seed crystal F on a seed crystal rod, discharging the seed crystal from the top of a crystal growth furnace, preheating the seed crystal on the surface of the mixed melt for 25 minutes, partially immersing the seed crystal below the liquid level, melting the seed crystal back in the mixed melt, keeping the temperature for 25 minutes, and rapidly cooling to the saturation temperature of 840 ℃;
then the temperature is reduced at the speed of 5 ℃/day, and the seed crystal is rotated at the rotating speed of 30rpmRod, after the crystal grows to the required size, the crystal is lifted off the surface of the melt, the temperature is reduced to the room temperature at the speed of 35 ℃/h, and then the crystal is taken out of the hearth, thus obtaining the Ba with the size of 22mm multiplied by 32mm multiplied by 20mm 3 La 4 B 3 O 13 And F, crystals.
The barium carbonate in the reaction formula can be replaced by barium fluoride or barium nitrate or barium oxalate or barium sulfate and other barium-containing salts or barium oxide or barium hydroxide, lanthanum oxide can be replaced by lanthanum carbonate or lanthanum nitrate or lanthanum chloride or lanthanum oxalate or lanthanum sulfate and other lanthanum-containing salts or lanthanum hydroxide, and boric acid can be replaced by boron oxide.
Example 9
Optional Ba obtained in examples 1 to 8 3 La 4 B 3 O 13 Processing a frequency multiplier with 5mm × 5mm × 6mm size by F crystal in matching direction, placing at 3 position as shown in FIG. 2, using a QNd: YAG laser as light source at room temperature, emitting infrared beam 2 with 1064nm wavelength from the QNd: YAG laser 1, and emitting Ba beam 3 La 4 B 3 O 13 And F, a single crystal 3 generates green frequency doubling light with the wavelength of 532nm, the output intensity is 6 times of KDP under the same condition, an emergent light beam 4 contains infrared light with the wavelength of 1064nm and green light with the wavelength of 532nm, and the green laser with the wavelength of 532nm is obtained after filtering by a filter 5.
Claims (10)
1. A compound barium lanthanum fluoborate is characterized in that the chemical formula of the compound is Ba 3 La 4 B 3 O 13 F。
2. The method for preparing the compound barium lanthanum fluoborate according to claim 1, which comprises the following steps: mixing a barium-containing compound, a lanthanum-containing compound, a boron-containing compound and a fluorine-containing compound to prepare the barium lanthanum fluoborate compound by a solid-phase reaction method, wherein the molar ratio of the element barium in the barium-containing compound, the element lanthanum in the lanthanum-containing compound, the element boron in the boron-containing compound and the element fluorine in the fluorine-containing compound is 2.8-3.2.
3. The method of claim 2, wherein the barium-containing compound comprises at least one of barium hydroxide, barium oxide, and barium salt;
the lanthanum-containing compound comprises at least one of lanthanum oxide, lanthanum hydroxide and lanthanum salt;
the boron-containing compound is at least one of boron oxide, boric acid and boron hydroxide;
the fluorine-containing compound is at least one of barium fluoride, lanthanum fluoride and ammonium fluoride.
4. The method for preparing the compound barium lanthanum fluoborate according to claim 3, wherein the barium salt comprises at least one of barium fluoride, barium carbonate, barium sulfate, barium phosphate, barium nitrate, barium nitrite, barium oxalate and barium acetate;
the lanthanum salt comprises at least one of lanthanum fluoride, lanthanum carbonate, lanthanum sulfate, lanthanum phosphate, lanthanum nitrate, lanthanum nitrite, lanthanum oxalate and lanthanum acetate.
5. 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, the space group is P63 (173), and the unit cell parameter is
The molecular weight is 1227.018.
6. The method for preparing a barium lanthanum fluoborate nonlinear optical crystal as claimed in claim 5, characterized in that the barium lanthanum fluoborate nonlinear optical crystal is grown by a high temperature melt method or a Czochralski method.
7. The method of claim 6, wherein the specific operations are performed by:
a. heating a mixture of the compound barium lanthanum fluoborate obtained in any one of claims 1 to 4 or the compound barium lanthanum fluoborate obtained in any one of claims 1 to 4 and a fluxing agent to melt to obtain a mixed melt, and cooling or growing at a constant temperature to prepare the barium lanthanum fluoborate nonlinear optical crystal;
or directly weighing the raw materials for preparing the compound barium lanthanum fluoborate according to the molar ratio or weighing the mixture of the raw materials for preparing the compound barium lanthanum fluoborate and the fluxing agent according to the molar ratio, heating to melt to obtain a mixed melt, and cooling or growing at constant temperature to prepare the barium lanthanum fluoborate nonlinear optical crystal;
b. b, placing the crucible containing the mixed melt prepared in the step a into a crystal growth furnace, fixing seed crystals on a seed crystal rod, putting the seed crystals down to be in contact with the liquid level of the mixed melt or in the mixed melt for remelting, and reducing the temperature to saturation temperature; cooling or growing at constant temperature to prepare the barium lanthanum fluoborate nonlinear optical crystal.
8. The method of claim 7, wherein the molar ratio of the compound barium lanthanum fluoborate to the flux is 1; or wherein the molar ratio of the barium-containing compound, lanthanum-containing compound, boron-containing compound and fluorine-containing compound to the flux is 2.8-3.2; the single fluxing agent comprises 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 comprises BaF 2 -H 3 BO 3 、PbO-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-Na 2 CO 3 -H 3 BO 3 、KF-K 2 CO 3 -H 3 BO 3 、KF-K 2 CO 3 -H 3 BO 3 -BaF 2 、NaF-Na 2 CO 3 -H 3 BO 3 、NaF-Na 2 CO 3 -H 3 BO 3 -BaF 2 、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 them.
9. The method according to claim 8, wherein the KF-H is a flux 3 BO 3 、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 fluoride to boric acid in the fluxing agent is 0.1-10; 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 carbonate to boric acid in the fluxing agent is 0.2-15; the KF-PbO and BaF 2 -molar ratio of fluoride to lead oxide in PbO, naF-PbO, liF-PbO fluxing agent is 0.5-19; 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 the PbO flux is 0.2-15; 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 the PbO flux is 0.1-10; 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 -the molar ratio of carbonate, boric acid and lead oxide in the PbO flux is from 1 to 13; the NaF-KF-H 3 BO 3 、NaF-BaF 2 -H 3 BO 3 、NaF-LiF-H 3 BO 3 、LiF-CaF 2 -H 3 BO 3 、LiF-BaF 2 -H 3 BO 3 The mol ratio of the first fluoride to the second fluoride to the boric acid in the fluxing agent is 0.1-21; 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 fluoride, carbonate and boric acid in the fluxing agent is 1-10; the KF-BaF 2 -Na 2 CO 3 -H 3 BO 3 、KF-BaF 2 -K 2 CO 3 -H 3 BO 3 、NaF-BaF 2 -Na 2 CO 3 -H 3 BO 3 、LiF-BaF 2 -Na 2 CO 3 -H 3 BO 3 First in fluxThe molar ratio of fluoride, second fluoride and carbonate to boric acid is 0.1-23.
10. The use of the barium lanthanum fluoborate nonlinear optical crystal according to claim 5, characterized in that the barium lanthanum fluoborate nonlinear optical crystal is used for preparing a frequency doubling converter.
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| CN102337586A (en) * | 2010-07-20 | 2012-02-01 | 中国科学院新疆理化技术研究所 | Compound barium borofluoride nonlinear optical crystal as well as preparation method and purposes thereof |
| US20120188630A1 (en) * | 2010-08-11 | 2012-07-26 | The Xinjiang Technical Institute of Physics & Chem Chinese Academy of Sciences | Potassium chloroborate nonlinear optical crystal, preparation method and use thereof |
| 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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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN102337586A (en) * | 2010-07-20 | 2012-02-01 | 中国科学院新疆理化技术研究所 | Compound barium borofluoride nonlinear optical crystal as well as preparation method and purposes thereof |
| US20120188630A1 (en) * | 2010-08-11 | 2012-07-26 | The Xinjiang Technical Institute of Physics & Chem Chinese Academy of Sciences | Potassium chloroborate nonlinear optical crystal, preparation method and use thereof |
| 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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