CN114604845B - Compound ammonium borophosphate fluoride and ammonium borophosphate fluoride nonlinear optical crystal, preparation method and application - Google Patents
Compound ammonium borophosphate fluoride and ammonium borophosphate fluoride nonlinear optical crystal, preparation method and application Download PDFInfo
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- CN114604845B CN114604845B CN202210336816.6A CN202210336816A CN114604845B CN 114604845 B CN114604845 B CN 114604845B CN 202210336816 A CN202210336816 A CN 202210336816A CN 114604845 B CN114604845 B CN 114604845B
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- 150000001875 compounds Chemical class 0.000 title claims abstract description 175
- 239000013078 crystal Substances 0.000 title claims abstract description 158
- 230000003287 optical effect Effects 0.000 title claims abstract description 63
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 title claims abstract description 30
- 238000002360 preparation method Methods 0.000 title claims abstract description 20
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 title claims abstract description 19
- 238000000034 method Methods 0.000 claims abstract description 33
- 238000010532 solid phase synthesis reaction Methods 0.000 claims abstract 2
- 239000010453 quartz Substances 0.000 claims description 119
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 119
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 76
- 238000007789 sealing Methods 0.000 claims description 75
- 238000010438 heat treatment Methods 0.000 claims description 74
- 238000001816 cooling Methods 0.000 claims description 56
- 238000002156 mixing Methods 0.000 claims description 39
- 229910052697 platinum Inorganic materials 0.000 claims description 38
- 238000001035 drying Methods 0.000 claims description 23
- 239000003795 chemical substances by application Substances 0.000 claims description 11
- 239000000126 substance Substances 0.000 claims description 7
- 229910019142 PO4 Inorganic materials 0.000 claims description 6
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims description 6
- 239000010452 phosphate Substances 0.000 claims description 6
- 238000007716 flux method Methods 0.000 claims description 5
- 238000003746 solid phase reaction Methods 0.000 claims description 4
- 238000004519 manufacturing process Methods 0.000 claims description 2
- -1 fluoride compound Chemical class 0.000 abstract description 2
- 239000000203 mixture Substances 0.000 description 24
- 239000000463 material Substances 0.000 description 17
- 229910052796 boron Inorganic materials 0.000 description 8
- 239000006184 cosolvent Substances 0.000 description 5
- 239000012071 phase Substances 0.000 description 3
- 230000005540 biological transmission Effects 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000004880 explosion Methods 0.000 description 1
- 238000013467 fragmentation Methods 0.000 description 1
- 238000006062 fragmentation reaction Methods 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000008204 material by function Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 231100000956 nontoxicity Toxicity 0.000 description 1
- 238000000206 photolithography Methods 0.000 description 1
- 238000005498 polishing Methods 0.000 description 1
- 238000001144 powder X-ray diffraction data Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000003595 spectral effect Effects 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 238000009461 vacuum packaging Methods 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B25/00—Phosphorus; Compounds thereof
- C01B25/16—Oxyacids of phosphorus; Salts thereof
- C01B25/26—Phosphates
- C01B25/455—Phosphates containing halogen
-
- 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
- C30B11/00—Single-crystal growth by normal freezing or freezing under temperature gradient, e.g. Bridgman-Stockbarger method
- C30B11/14—Single-crystal growth by normal freezing or freezing under temperature gradient, e.g. Bridgman-Stockbarger method characterised by the seed, e.g. its crystallographic orientation
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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
- C30B29/12—Halides
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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
- 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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- C—CHEMISTRY; METALLURGY
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- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/30—Three-dimensional structures
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- C01P2002/00—Crystal-structural characteristics
- C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
- C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
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- C01P2002/00—Crystal-structural characteristics
- C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
- C01P2002/76—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by a space-group or by other symmetry indications
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- C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
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Abstract
The invention relates to an ammonium borophosphate fluoride compound, an ammonium borophosphate fluoride nonlinear optical crystal, a preparation method and application thereof, wherein the molecular formula of the compound is (NH) 4 ) 3 B 11 PO 19 F 3 The molecular weight is 565.01, and the preparation is carried out by adopting a solid phase method; the molecular formula of the crystal is (NH) 4 ) 3 B 11 PO 19 F 3 The molecular weight is 565.01, the crystal belongs to a trigonal system, and the space group isR3, the unit cell parameters area=b=11.3782(17)Å,c=11.912(3)Å,Z=3,α=β=90°,γ=120°,V=1335.6(5)Å 3 . The preparation method adopts a fluxing agent method or a crucible descending method. By this method (NH) with dimensions of the order of centimeters is obtained 4 ) 3 B 11 PO 19 F 3 The nonlinear optical crystal can be used as an ultraviolet and deep ultraviolet nonlinear optical crystal to be applied to all-solid-state lasers.
Description
Technical Field
The invention relates to a compound ammonium borofluoride phosphate (NH) 4 ) 3 B 11 PO 19 F 3 And ammonium borofluoride phosphate (NH) 4 ) 3 B 11 PO 19 F 3 Nonlinear optical crystal, preparation method and application thereof.
Background
Nonlinear optical crystals are very important optical functional materials that can extend the limited spectral output range of lasers. With the rapid development of photolithography technology, laser processing and other industries, the requirement for nonlinear optical crystals is growing increasingly, and the development of all-solid-state laser sources has become a domestic and foreign laser sourceOne hotspot in research in the optical field. Due to the transmission band limitation of the crystals, the applicable band of each crystal is different, and the nonlinear optical crystals applicable to ultraviolet and deep ultraviolet bands are fewer. In the ultraviolet band, the industrialized nonlinear optical crystal has LiB 3 O 5 (LBO)、CsB 3 O 5 (CBO)、CsLiB 6 O 10 (CLBO) and Low temperature phase BaB 2 O 4 (beta-BBO) and the like. However, LBO, CBO and CLBO have small birefringence and cannot achieve phase matching in the deep ultraviolet band. And BBO crystals cannot realize phase matching of deep ultraviolet band due to walk-off effect. In the deep ultraviolet band below 200nm, KBe 2 BO 3 F 2 (KBBF) is the only nonlinear optical crystal which can be practically used at present, but the application of the nonlinear optical crystal is limited due to lamellar growth habit and toxic raw materials. Therefore, it is necessary to search for a novel ultraviolet nonlinear optical crystal having more excellent properties.
Disclosure of Invention
The invention aims at providing a compound ammonium borophosphate fluoride, wherein the chemical formula of the compound is (NH) 4 ) 3 B 11 PO 19 F 3 The molecular weight is 565.01, and the preparation method is a solid phase reaction method.
Another object of the present invention is to provide a non-linear optical crystal of ammonium borophosphate fluoride having the chemical formula (NH) 4 ) 3 B 11 PO 19 F 3 The molecular weight is 565.01, the crystal belongs to a trigonal system, the space group is R3, and the unit cell parameter is Z=3,α=β=90°,γ=120°,/>
The invention also aims to provide a preparation method of the ammonium fluoborophosphate nonlinear optical crystal, which is prepared by adopting a cosolvent method or a crucible descending method.
It is a further object of the present invention to provide the use of ammonium borofluoride nonlinear optical crystals.
The invention relates to a compound ammonium borofluoride phosphate, the chemical formula of which is (NH) 4 ) 3 B 11 PO 19 F 3 The molecular weight is 565.01, and the preparation method is a solid phase reaction method.
The preparation method of the compound ammonium borofluoride phosphate adopts a solid phase reaction method, and comprises the following specific operations:
in mole ratio of NH 4 B: P: F=3-7:12-24:1-2:6-12 will contain NH 4 The compound being NH 4 PF 6 And (NH) 4 ) 2 CO 3 Or NH 4 PF 6 And NH 4 HCO 3 The B-containing compound being H 3 BO 3 Or B is a 2 O 3 The P-containing compound being NH 4 PF 6 The F-containing compound being NH 4 PF 6 Mixing, sealing in a high-pressure hydrothermal kettle or quartz tube, heating to 380-500deg.C at a rate of 10-20deg.C/h, maintaining for 1-5 days, cooling to 30deg.C at a rate of 0.5-2deg.C/h, and opening the kettle or quartz tube to obtain compound (NH) 4 ) 3 B 11 PO 19 F 3 。
Ammonium borophosphate fluoride nonlinear optical crystal, the chemical formula of the crystal is (NH) 4 ) 3 B 11 PO 19 F 3 The molecular weight is 565.01, the crystal belongs to a trigonal system, the space group is R3, and the unit cell parameter isZ=3,α=β=90°,γ=120°,/>
The preparation method of the ammonium borophosphate fluoride nonlinear optical crystal adopts a fluxing agent method or a crucible descending method:
the method adopts a fluxing agent method to grow crystals, and comprises the following steps:
a. in mole ratio of NH 4 B: P: F=3-7:12-24:1-2:6-12 will contain NH 4 The compound being NH 4 PF 6 And (NH) 4 ) 2 CO 3 Or NH 4 PF 6 And NH 4 HCO 3 The B-containing compound being H 3 BO 3 Or B is a 2 O 3 The P-containing compound being NH 4 PF 6 The F-containing compound being NH 4 PF 6 Mixing, sealing in a high-pressure hydrothermal kettle or quartz tube, heating to 380-500deg.C at a rate of 10-20deg.C/h, maintaining for 1-5 days, cooling to 30deg.C at a rate of 0.5-2deg.C/h, and opening the kettle or quartz tube to obtain compound (NH) 4 ) 3 B 11 PO 19 F 3 ;
b. The compound (NH) obtained in step a 4 ) 3 B 11 PO 19 F 3 Sealing in a high-pressure hydrothermal kettle or quartz tube, heating to 400-500deg.C at a rate of 10-20deg.C/h, keeping for 1-5 days, cooling to 30deg.C at a rate of 0.5-2deg.C/h, and opening the kettle or quartz tube to obtain (NH) 4 ) 3 B 11 PO 19 F 3 Seed crystal of the crystal;
c. placing the seed crystal obtained in step b at the bottom of a high-pressure hydrothermal kettle or quartz tube, and then placing the compound (NH) 4 ) 3 B 11 PO 19 F 3 With fluxing agent NH 4 PF 6 、NH 4 HCO 3 And B 2 O 3 Mixing, sealing in high-pressure hydrothermal kettle or quartz tube, wherein the fluxing agent NH 4 PF 6 、NH 4 HCO 3 And B 2 O 3 The molar ratio of (2) to (6) is 1:2:6;
d. c, placing the high-pressure hydrothermal kettle or the quartz tube in the step c in a muffle furnace or a drying oven, heating to 400-500 ℃ at the speed of 10-20 ℃/h, keeping the temperature for 1-5 days, slowly cooling to 30 ℃ at the speed of 0.5-2 ℃/h, and opening the high-pressure hydrothermal kettle or the quartz tube to obtain the centimeter-level product(NH 4 ) 3 B 11 PO 19 F 3 A nonlinear optical crystal;
the crystal is grown by adopting a crucible descent method, and the specific operation comprises the following steps:
a. in mole ratio of NH 4 B: P: F=3-7:12-24:1-2:6-12 will contain NH 4 The compound being NH 4 PF 6 And (NH) 4 ) 2 CO 3 Or NH 4 PF 6 And NH 4 HCO 3 The B-containing compound being H 3 BO 3 Or B is a 2 O 3 The P-containing compound being NH 4 PF 6 The F-containing compound being NH 4 PF 6 Mixing, sealing in a high-pressure hydrothermal kettle or quartz tube, heating to 380-500deg.C at a rate of 10-20deg.C/h, maintaining for 1-5 days, cooling to 30deg.C at a rate of 0.5-2deg.C/h, and opening the kettle or quartz tube to obtain compound (NH) 4 ) 3 B 11 PO 19 F 3 ;
b. The compound (NH) obtained in step a 4 ) 3 B 11 PO 19 F 3 Sealing in a high-pressure hydrothermal kettle or quartz tube, heating to 400-500deg.C at a rate of 10-20deg.C/h, keeping for 1-5 days, cooling to 30deg.C at a rate of 0.5-2deg.C/h, and opening the kettle or quartz tube to obtain (NH) 4 ) 3 B 11 PO 19 F 3 Seed crystal of the crystal;
c. placing the seed crystal obtained in step b at the bottom of a platinum crucible or quartz tube, and then placing the compound (NH) obtained in step a 4 ) 3 B 11 PO 19 F 3 Placing into a platinum crucible or a quartz tube for sealing;
d. c, placing the platinum crucible or the quartz tube in the step c in a crucible descending furnace, heating to 400-500 ℃ at a speed of 10-20 ℃/h, keeping the temperature for 1-5 days, and slowly reducing the platinum crucible or the quartz tube at a speed of 0.5-2 mm/h; simultaneously, keeping the growth temperature unchanged or slowly reducing the temperature at the speed of 0.5-2 ℃/h, reducing the temperature of a growth furnace to 30 ℃ after the growth is finished, opening a platinum crucible or a quartz tube,thus, cm-level (NH) 4 ) 3 B 11 PO 19 F 3 Nonlinear optical crystal.
Use of the ammonium borophosphate fluoride nonlinear optical crystal in the preparation of multiband frequency doubling devices or optical elements.
The ammonium boron fluoride phosphate nonlinear optical crystal is used for preparing harmonic light output of 2 times or 3 times or 4 times or 5 times of 1064nm fundamental frequency light output by a YAG laser.
The use of the ammonium borophosphate fluoride nonlinear optical crystal in the preparation of a deep ultraviolet frequency doubling light output generating ultraviolet frequency doubling light or below 200 nm.
The use of the ammonium borophosphate nonlinear optical crystal in the preparation of a frequency multiplication generator, an upper or lower frequency converter or an optical parametric oscillator.
The invention relates to a preparation method of ammonium fluoborophosphate nonlinear optical crystal, wherein the lining of a high-pressure hydrothermal kettle used in the method is a gold or platinum sleeve. When the container is a quartz tube, a flame gun is needed to be used for vacuum packaging before sealing to avoid the explosion of the quartz tube caused by gas released in the reaction process, and the vacuum degree is 1 multiplied by 10 -3 Pa。
The invention relates to a preparation method of ammonium borophosphate fluoride nonlinear optical crystal, which is used for obtaining (NH) with the size of centimeter level 4 ) 3 B 11 PO 19 F 3 Nonlinear optical crystal, using a large-sized container and extending the crystal growth period, can obtain a correspondingly large-sized nonlinear optical crystal (NH) 4 ) 3 B 11 PO 19 F 3 . At the (NH) 4 ) 3 B 11 PO 19 F 3 The nonlinear optical crystal is easy to grow and transparent without wrapping in the growth process, and has the advantages of high growth speed, low cost, no toxicity, easy obtainment of large-size crystals and the like.
The preparation method of the ammonium borophosphate fluoride nonlinear optical crystal of the invention can obtain large-size (NH) 4 ) 3 B 11 PO 19 F 3 Nonlinear optical crystal, based on crystallographic number of crystalAccording to the above, the crystal blank is oriented, the crystal is cut according to the required angle, thickness and cross-sectional size, the light-passing surface of the crystal is polished, and the crystal blank can be used as a nonlinear optical device, the (NH) 4 ) 3 B 11 PO 19 F 3 The nonlinear optical crystal has the advantages of wider light transmission wave band, stable physical and chemical properties, high mechanical hardness, difficult fragmentation, easy cutting, polishing and storage, and the like.
Drawings
FIG. 1 shows a compound (NH) of the present invention 4 ) 3 B 11 PO 19 F 3 The powder XRD pattern of (C) is consistent with the theoretical XRD pattern, and proves that the compound (NH) 4 ) 3 B 11 PO 19 F 3 Is present;
FIG. 2 shows the process of the present invention (NH 4 ) 3 B 11 PO 19 F 3 Structure of the crystal;
FIG. 3 shows the (NH) of the present invention 4 ) 3 B 11 PO 19 F 3 The working principle diagram of a nonlinear optical device for crystal production is shown in the specification, wherein 1 is a laser, 2 is an emitted light beam, and 3 is (NH 4 ) 3 B 11 PO 19 F 3 The crystal, 4 is the outgoing light beam, 5 is the filter.
Detailed Description
The invention is further described below with reference to examples. It should be noted that the following examples should not be construed as limiting the scope of the invention, and any modifications made thereto do not depart from the spirit of the invention. The materials and equipment used in the present invention are commercially available unless otherwise specified.
Example 1
NH is added to 4 PF 6 ,NH 4 HCO 3 ,B 2 O 3 Mixing at a molar ratio of 1:2:6, sealing in a quartz tube, placing in a muffle furnace, heating to 400deg.C at 10deg.C/h, keeping the temperature for 2 days, cooling to 30deg.C at 0.5deg.C/h, and opening the quartz tube to obtain the compound (NH) 4 ) 3 B 11 PO 19 F 3 。
Example 2
NH is added to 4 PF 6 ,NH 4 HCO 3 ,B 2 O 3 Mixing at a molar ratio of 1:2:6, sealing in a quartz tube, placing in a muffle furnace, heating to 150deg.C at 15 ℃/h, keeping the temperature for 3 days, cooling to 30deg.C at 2 ℃/h, and opening the quartz tube to obtain the compound (NH) 4 ) 3 B 11 PO 19 F 3 。
Example 3
NH is added to 4 PF 6 ,NH 4 HCO 3 ,B 2 O 3 Mixing at a molar ratio of 2:5:12, sealing in a high-pressure hydrothermal kettle, placing in a drying oven, heating to 500deg.C at a rate of 20deg.C/h, keeping the temperature for 2 days, cooling to 30deg.C at a rate of 1deg.C/h, and opening the high-pressure hydrothermal kettle to obtain compound (NH) 4 ) 3 B 11 PO 19 F 3 。
Example 4
NH is added to 4 PF 6 ,NH 4 HCO 3 ,B 2 O 3 Mixing at a molar ratio of 2:5:12, sealing in a high-pressure hydrothermal kettle, placing in a drying oven, heating to 410 deg.C at a rate of 18 deg.C/h, keeping the temperature for 1 day, cooling to 30 deg.C at a rate of 0.5 deg.C/h, and opening the high-pressure hydrothermal kettle to obtain the compound (NH) 4 ) 3 B 11 PO 19 F 3 。
Example 5
NH is added to 4 PF 6 ,NH 4 HCO 3 ,H 3 BO 3 Mixing at a molar ratio of 1:2:12, sealing in a high-pressure hydrothermal kettle, placing in a drying oven, heating to 400deg.C at 15 ℃/h, keeping the temperature for 2 days, cooling to 30deg.C at 0.5 ℃/h, and opening the high-pressure hydrothermal kettle to obtain the compound (NH) 4 ) 3 B 11 PO 19 F 3 。
Example 6
NH is added to 4 PF 6 ,NH 4 HCO 3 ,H 3 BO 3 By moleMixing at a ratio of 1:2:12, sealing in a high-pressure hydrothermal kettle, placing in a drying oven, heating to 440 deg.C at a rate of 10deg.C/h, keeping the temperature for 2 days, cooling to 30deg.C at a rate of 1.5deg.C/h, and opening the high-pressure hydrothermal kettle to obtain compound (NH) 4 ) 3 B 11 PO 19 F 3 。
Example 7
NH is added to 4 PF 6 ,(NH 4 ) 2 CO 3 ,B 2 O 3 Mixing at a molar ratio of 1:1:6, sealing in a quartz tube, placing in a muffle furnace, heating to 380deg.C at a rate of 13deg.C/h, keeping the temperature for 1 day, cooling to 30deg.C at a rate of 1deg.C/h, and opening the quartz tube to obtain the compound (NH) 4 ) 3 B 11 PO 19 F 3 。
Example 8
NH is added to 4 PF 6 ,(NH 4 ) 2 CO 3 ,B 2 O 3 Mixing at a molar ratio of 1:1:6, sealing in a quartz tube, placing in a muffle furnace, heating to 380deg.C at a rate of 20deg.C/h, keeping the temperature for 4 days, cooling to 30deg.C at a rate of 2deg.C/h, and opening the quartz tube to obtain the compound (NH) 4 ) 3 B 11 PO 19 F 3 。
Example 9
NH is added to 4 PF 6 ,(NH 4 ) 2 CO 3 ,B 2 O 3 Mixing at a molar ratio of 1:1:6, sealing in a high-pressure hydrothermal kettle, placing in a drying oven, heating to 1200deg.C at a rate of 13deg.C/h, keeping the temperature for 3 days, cooling to 30deg.C at a rate of 1deg.C/h, and opening the high-pressure hydrothermal kettle to obtain compound (NH) 4 ) 3 B 11 PO 19 F 3 。
Example 10
NH is added to 4 PF 6 ,(NH 4 ) 2 CO 3 ,B 2 O 3 Mixing at a molar ratio of 1:1:6, sealing in a high-pressure hydrothermal kettle, placing in a drying oven, heating to 500 deg.C at a rate of 16 deg.C/h, keeping the temperature for 3 days, and heating at the same temperatureReducing the speed of 1.5 ℃/h to 30 ℃, and opening a high-pressure hydrothermal kettle to obtain the compound (NH) 4 ) 3 B 11 PO 19 F 3 。
Example 11
NH is added to 4 PF 6 ,(NH 4 ) 2 CO 3 ,H 3 BO 3 Mixing at a molar ratio of 1:1:12, sealing in a high-pressure hydrothermal kettle, placing in a drying oven, heating to 500deg.C at a rate of 12deg.C/h, keeping the temperature for 2 days, cooling to 30deg.C at a rate of 0.5deg.C/h, and opening the high-pressure hydrothermal kettle to obtain compound (NH) 4 ) 3 B 11 PO 19 F 3 。
Example 12
NH is added to 4 PF 6 ,(NH 4 ) 2 CO 3 ,H 3 BO 3 Mixing at a molar ratio of 1:1:12, sealing in a high-pressure hydrothermal kettle, placing in a drying oven, heating to 450deg.C at a rate of 20deg.C/h, keeping the temperature for 1 day, cooling to 30deg.C at a rate of 2deg.C/h, and opening the high-pressure hydrothermal kettle to obtain compound (NH) 4 ) 3 B 11 PO 19 F 3 。
Example 13
Growth by flux method (NH) 4 ) 3 B 11 PO 19 F 3 A crystal:
a. in mole ratio of NH 4 NH is contained in the mixture of the components B, P, F=3:12:1:6 4 The compound being NH 4 PF 6 And (NH) 4 ) 2 CO 3 The compound containing B is B 2 O 3 The P-containing compound being NH 4 PF 6 The F-containing compound being NH 4 PF 6 Mixing, sealing in a high-pressure hydrothermal kettle, placing in a drying oven, heating to 500deg.C at 10deg.C/h, keeping the temperature for 1 day, cooling to 30deg.C at 0.5deg.C/h, and opening the high-pressure hydrothermal kettle to obtain compound (NH) 4 ) 3 B 11 PO 19 F 3 ;
b. The compound (NH) obtained in step a 4 ) 3 B 11 PO 19 F 3 Sealing in a high-pressure hydrothermal kettle, heating to 400deg.C at 10deg.C/h, maintaining the temperature for 4 days, cooling to 30deg.C at 2deg.C/h, and opening the high-pressure hydrothermal kettle to obtain (NH) 4 ) 3 B 11 PO 19 F 3 Seed crystal of the crystal;
c. placing the seed crystal obtained in the step b at the bottom of a high-pressure hydrothermal kettle, and then placing the compound (NH) 4 ) 3 B 11 PO 19 F 3 With fluxing agent NH 4 PF 6 、NH 4 HCO 3 And B 2 O 3 Mixing, placing into a high-pressure hydrothermal kettle, and sealing, wherein the cosolvent NH 4 PF 6 、NH 4 HCO 3 And B 2 O 3 The molar ratio of (2) to (6) is 1:2:6;
d. placing the high-pressure hydrothermal kettle in the step c into a drying oven, heating to 400 ℃ at the speed of 10 ℃/h, keeping the temperature for 5 days, then cooling to 30 ℃ at the speed of 2 ℃/day, and opening the high-pressure hydrothermal kettle to obtain the (NH) with the size of phi 11mm multiplied by 10mm multiplied by 4mm 4 ) 3 B 11 PO 19 F 3 Nonlinear optical crystal.
Example 14
Growth by flux method (NH) 4 ) 3 B 11 PO 19 F 3 A crystal:
a. will contain NH 4 The compound being NH 4 PF 6 And NH 4 HCO 3 The B-containing compound being H 3 BO 3 The P-containing compound being NH 4 PF 6 The F-containing compound being NH 4 PF 6 In mole ratio of NH 4 Mixing the materials uniformly in a ratio of (B) to (P) and (F=7:24:2:12), sealing in a quartz tube, placing in a muffle furnace, heating to 380 ℃ at a speed of 20 ℃/h, keeping the temperature for 5 days, then cooling to 30 ℃ at a speed of 2 ℃/h, and opening the quartz tube to obtain the compound (NH) 4 ) 3 B 11 PO 19 F 3 ;
b. The compound (NH) obtained in step a 4 ) 3 B 11 PO 19 F 3 Sealing in high pressure hydrothermal kettle, and drying at 20deg.CHeating to 500 ℃ at the rate of/h, keeping the temperature for 1 day, then cooling to 30 ℃ at the rate of 0.5 ℃/h, and opening the high-pressure hydrothermal kettle to obtain (NH) 4 ) 3 B 11 PO 19 F 3 Seed crystal of the crystal;
c. placing the seed crystal obtained in the step b at the bottom of a high-pressure hydrothermal kettle, and then placing the compound (NH) 4 ) 3 B 11 PO 19 F 3 With fluxing agent NH 4 PF 6 、NH 4 HCO 3 And B 2 O 3 Mixing, placing into a high-pressure hydrothermal kettle, and sealing, wherein the cosolvent NH 4 PF 6 、NH 4 HCO 3 And B 2 O 3 The molar ratio of (2) to (6) is 1:2:6;
d. placing the high-pressure hydrothermal kettle in the step c into a drying oven, heating to 500 ℃ at the speed of 20 ℃/h, keeping the temperature for 1 day, then cooling to 30 ℃ at the speed of 0.5 ℃/day, and opening the high-pressure hydrothermal kettle to obtain the (NH) with the size of phi 14mm multiplied by 11mm multiplied by 6mm 4 ) 3 B 11 PO 19 F 3 Nonlinear optical crystal.
Example 15
Growth by flux method (NH) 4 ) 3 B 11 PO 19 F 3 A crystal:
a. will contain NH 4 The compound being NH 4 PF 6 And (NH) 4 ) 2 CO 3 The compound containing B is B 2 O 3 The P-containing compound being NH 4 PF 6 The F-containing compound being NH 4 PF 6 In mole ratio of NH 4 Mixing the materials uniformly with the ratio of B, P and F=3:11:1:6, filling the mixture into a high-pressure hydrothermal kettle, sealing the kettle, placing the kettle into a drying oven, heating the kettle to 450 ℃ at the speed of 15 ℃/h, keeping the temperature for 3 days, then cooling the kettle to 30 ℃ at the speed of 1.5 ℃/h, and opening the high-pressure hydrothermal kettle to obtain the compound (NH) 4 ) 3 B 11 PO 19 F 3 。
b. The compound (NH) obtained in step a 4 ) 3 B 11 PO 19 F 3 Sealing in quartz tube, putting into muffle furnace, heating to 400deg.C at 15 deg.C/h, and keeping constantThe temperature is reduced to 30 ℃ at the speed of 2 ℃/h after 2 days, and the quartz tube is opened to obtain (NH) 4 ) 3 B 11 PO 19 F 3 Seed crystal of the crystal;
c. placing the seed crystal obtained in the step b at the bottom of a high-pressure hydrothermal kettle, and then placing the compound (NH) 4 ) 3 B 11 PO 19 F 3 With fluxing agent NH 4 PF 6 、NH 4 HCO 3 And B 2 O 3 Mixing, placing into quartz tube, sealing, wherein cosolvent NH 4 PF 6 、NH 4 HCO 3 And B 2 O 3 The molar ratio of (2) to (6) is 1:2:6;
d. putting the quartz tube in the step c into a muffle furnace, heating to 400 ℃ at the speed of 10 ℃/h, keeping the temperature for 5 days, then cooling to 30 ℃ at the speed of 2 ℃/day, and opening a high-pressure hydrothermal kettle to obtain the (NH) with the size of phi 12mm multiplied by 10mm multiplied by 4mm 4 ) 3 B 11 PO 19 F 3 Nonlinear optical crystal.
Example 16
Growth by flux method (NH) 4 ) 3 B 11 PO 19 F 3 A crystal:
a. will contain NH 4 The compound being NH 4 PF 6 And NH 4 HCO 3 The B-containing compound being H 3 BO 3 The P-containing compound being NH 4 PF 6 The F-containing compound being NH 4 PF 6 In mole ratio of NH 4 Mixing the materials uniformly in a ratio of (B) to (P) and (F=7:24:2:12), sealing in a quartz tube, placing in a muffle furnace, heating to 410 ℃ at a speed of 13 ℃/h, keeping the temperature for 2 days, then cooling to 30 ℃ at a speed of 1 ℃/h, and opening the quartz tube to obtain the compound (NH) 4 ) 3 B 11 PO 19 F 3 。
b. The compound (NH) obtained in step a 4 ) 3 B 11 PO 19 F 3 Sealing in quartz tube, heating to 480 deg.C at 17 deg.C/h, maintaining for 1 day, cooling to 30 deg.C at 0.5 deg.C/h, and opening quartz tube to obtain (NH) 4 ) 3 B 11 PO 19 F 3 Seed crystal of the crystal;
c. placing the seed crystal obtained in the step b at the bottom of a quartz tube, and then placing the compound (NH) 4 ) 3 B 11 PO 19 F 3 With fluxing agent NH 4 PF 6 、NH 4 HCO 3 And B 2 O 3 Mixing, placing into quartz tube, sealing, wherein cosolvent NH 4 PF 6 、NH 4 HCO 3 And B 2 O 3 The molar ratio of (2) to (6) is 1:2:6;
d. putting the quartz tube in the step c into a muffle furnace, heating to 500 ℃ at the speed of 18 ℃/h, keeping the temperature for 1 day, then cooling to 30 ℃ at the speed of 0.5 ℃/day, and opening a high-pressure hydrothermal kettle to obtain the (NH) with the size of phi 13mm multiplied by 15mm multiplied by 4mm 4 ) 3 B 11 PO 19 F 3 Nonlinear optical crystal.
Example 17
Growth by crucible descent method (NH) 4 ) 3 B 11 PO 19 F 3 A crystal:
a. will contain NH 4 The compound being NH 4 PF 6 And (NH) 4 ) 2 CO 3 The compound containing B is B 2 O 3 The P-containing compound being NH 4 PF 6 The F-containing compound being NH 4 PF 6 In mole ratio of NH 4 Mixing the materials uniformly with the ratio of B, P and F=3:12:1:6, filling the mixture into a high-pressure hydrothermal kettle, sealing the kettle, placing the kettle into a drying oven, heating the kettle to 500 ℃ at the speed of 10 ℃/h, keeping the temperature for 2 days, then cooling the kettle to 30 ℃ at the speed of 0.5 ℃/h, and opening the high-pressure hydrothermal kettle to obtain the compound (NH) 4 ) 3 B 11 PO 19 F 3 ;
b. The compound (NH) obtained in step a 4 ) 3 B 11 PO 19 F 3 Sealing in a high-pressure hydrothermal kettle, heating to 500deg.C at 20deg.C/h, maintaining the temperature for 3 days, cooling to 30deg.C at 0.5deg.C/h, and opening the high-pressure hydrothermal kettle to obtain (NH) 4 ) 3 B 11 PO 19 F 3 Seed crystal of the crystal;
c. subjecting the mixture obtained in step b (NH 4 ) 3 B 11 PO 19 F 3 Seed crystals are placed at the bottom of a platinum crucible, and then the compound (NH) obtained in step a 4 ) 3 B 11 PO 19 F 3 Placing into a platinum crucible for sealing;
d. placing the platinum crucible in the step c into a crucible descending furnace, heating to 400 ℃ at the speed of 10 ℃/h, preserving heat for 5 days, slowly reducing the platinum crucible at the speed of 2mm/h while keeping the growth temperature unchanged, reducing the temperature of the growth furnace to 30 ℃ after the growth is finished, and taking out the platinum crucible to obtain the (NH) with the size of phi 16mm multiplied by 15mm multiplied by 5mm 4 ) 3 B 11 PO 19 F 3 Nonlinear optical crystal.
Example 18
Growth by crucible descent method (NH) 4 ) 3 B 11 PO 19 F 3 A crystal:
a. will contain NH 4 The compound being NH 4 PF 6 And NH 4 HCO 3 The B-containing compound being H 3 BO 3 The P-containing compound being NH 4 PF 6 The F-containing compound being NH 4 PF 6 In mole ratio of NH 4 Mixing the materials uniformly in a ratio of (B) to (P) and (F=7:24:2:12), sealing in a quartz tube, placing in a muffle furnace, heating to 400 ℃ at a speed of 15 ℃/h, keeping the temperature for 4 days, then cooling to 30 ℃ at a speed of 2 ℃/h, and opening the quartz tube to obtain the compound (NH) 4 ) 3 B 11 PO 19 F 3 ;
b. The compound (NH) obtained in step a 4 ) 3 B 11 PO 19 F 3 Sealing in a high-pressure hydrothermal kettle, placing in a drying oven, heating to 400 ℃ at a speed of 16 ℃/h, keeping the temperature for 5 days, and then cooling to 30 ℃ at a speed of 2 ℃/h; opening the high-pressure hydrothermal kettle to obtain (NH) 4 ) 3 B 11 PO 19 F 3 Seed crystal of the crystal;
c. subjecting the mixture obtained in step b (NH 4 ) 3 B 11 PO 19 F 3 Seed crystals are placed at the bottom of a platinum crucible, and then the compound (NH) obtained in step a 4 ) 3 B 11 PO 19 F 3 Placing into a platinum crucible for sealing;
d. placing the platinum crucible in the step c into a crucible descending furnace, heating to 470 ℃ at a speed of 15 ℃/h, preserving heat for 1 day, slowly reducing the platinum crucible at a speed of 0.5mm/h while keeping the growth temperature unchanged, reducing the temperature of the growth furnace to 30 ℃ after the growth is finished, and taking out the platinum crucible to obtain the (NH) with the size of phi 12mm multiplied by 13mm multiplied by 5mm 4 ) 3 B 11 PO 19 F 3 Nonlinear optical crystal.
Example 19
Growth by crucible descent method (NH) 4 ) 3 B 11 PO 19 F 3 A crystal:
a. will contain NH 4 The compound being NH 4 PF 6 ,(NH 4 ) 2 CO 3 The compound containing B is B 2 O 3 The P-containing compound being NH 4 PF 6 The F-containing compound being NH 4 PF 6 In mole ratio of NH 4 Mixing the materials uniformly with the ratio of B, P and F=3:11:1:6, filling the mixture into a high-pressure hydrothermal kettle, sealing the kettle, placing the kettle into a drying oven, heating the kettle to 480 ℃ at the speed of 12 ℃/h, keeping the temperature for 2 days, then cooling the kettle to 30 ℃ at the speed of 1.5 ℃/h, and opening the high-pressure hydrothermal kettle to obtain the compound (NH) 4 ) 3 B 11 PO 19 F 3 ;
b. The compound (NH) obtained in step a 4 ) 3 B 11 PO 19 F 3 Sealing in a high-pressure hydrothermal kettle, placing in a drying oven, heating to 500 ℃ at a speed of 14 ℃/h, keeping the temperature for 1 day, and then cooling to 30 ℃ at a speed of 0.5 ℃/h; opening the high-pressure hydrothermal kettle to obtain (NH) 4 ) 3 B 11 PO 19 F 3 Seed crystal of the crystal;
c. subjecting the mixture obtained in step b (NH 4 ) 3 B 11 PO 19 F 3 Seed crystals are placed at the bottom of a platinum crucible, and then the compound (NH) obtained in step a 4 ) 3 B 11 PO 19 F 3 Placing into a platinum crucible for sealing;
d. placing the platinum crucible in the step c into a crucible descending furnace, heating to 400 ℃ at the speed of 10 ℃/h, preserving heat for 5 days, slowly reducing the platinum crucible at the speed of 2mm/h, slowly reducing the temperature at the speed of 0.5 ℃/h, after the growth is finished, reducing the temperature of the growth furnace to 30 ℃, and taking out the platinum crucible to obtain the (NH) with the size of phi 16mm multiplied by 14mm multiplied by 5mm 4 ) 3 B 11 PO 19 F 3 Nonlinear optical crystal.
Example 20
Growth by crucible descent method (NH) 4 ) 3 B 11 PO 19 F 3 A crystal:
a. will contain NH 4 The compound being NH 4 PF 6 And NH 4 HCO 3 The B-containing compound being H 3 BO 3 The P-containing compound being NH 4 PF 6 The F-containing compound being NH 4 PF 6 In mole ratio of NH 4 Mixing the materials uniformly with ratio of B, P, F=7:24:2:12, sealing in a quartz tube, placing in a muffle furnace, heating to 470 ℃ at a speed of 16 ℃/h, keeping the temperature for 2 days, then cooling to 30 ℃ at a speed of 1 ℃/h, and opening the quartz tube to obtain the compound (NH) 4 ) 3 B 11 PO 19 F 3 ;
b. The compound (NH) obtained in step a 4 ) 3 B 11 PO 19 F 3 Sealing in a high-pressure hydrothermal kettle, heating to 400deg.C at a rate of 12deg.C/h, maintaining the temperature for 2 days, cooling to 30deg.C at a rate of 2deg.C/h, and opening the high-pressure hydrothermal kettle to obtain (NH) 4 ) 3 B 11 PO 19 F 3 Seed crystal of the crystal;
c. subjecting the mixture obtained in step b (NH 4 ) 3 B 11 PO 19 F 3 Seed crystals are placed at the bottom of a platinum crucible, and then the compound (NH) obtained in step a 4 ) 3 B 11 PO 19 F 3 Placing into a platinum crucible for sealing;
d. the step cPlacing a platinum crucible in a crucible descending furnace, heating to 500 ℃ at a speed of 20 ℃/h, preserving heat for 4 days, slowly reducing the platinum crucible at a speed of 0.5mm/h, slowly reducing the temperature at a speed of 0.5 ℃/h, after the growth is finished, reducing the temperature of the growth furnace to 30 ℃, taking out the platinum crucible, and obtaining the (NH) with the size of phi 13mm multiplied by 14mm multiplied by 5mm 4 ) 3 B 11 PO 19 F 3 Nonlinear optical crystal.
Example 21
Growth by crucible descent method (NH) 4 ) 3 B 11 PO 19 F 3 A crystal:
a. will contain NH 4 The compound being NH 4 PF 6 And (NH) 4 ) 2 CO 3 The compound containing B is B 2 O 3 The P-containing compound being NH 4 PF 6 The F-containing compound being NH 4 PF 6 In mole ratio of NH 4 Mixing the materials uniformly with the ratio of B, P and F=3:12:1:6, filling the mixture into a high-pressure hydrothermal kettle, sealing the kettle, placing the kettle into a drying oven, heating the kettle to 500 ℃ at the speed of 14 ℃/h, keeping the temperature for 1 day, then reducing the kettle to 30 ℃ at the speed of 0.5 ℃/h, and opening the high-pressure hydrothermal kettle to obtain the compound (NH) 4 ) 3 B 11 PO 19 F 3 ;
b. The compound (NH) obtained in step a 4 ) 3 B 11 PO 19 F 3 Sealing in a high-pressure hydrothermal kettle, heating to 500 deg.C at 20 deg.C/h, maintaining the temperature for 1 day, cooling to 30 deg.C at 0.5 deg.C/h, and opening the high-pressure hydrothermal kettle to obtain (NH) 4 ) 3 B 11 PO 19 F 3 Seed crystal of the crystal;
c. subjecting the mixture obtained in step b (NH 4 ) 3 B 11 PO 19 F 3 Seed crystals are placed at the bottom of a platinum crucible, and then the compound (NH) obtained in step a 4 ) 3 B 11 PO 19 F 3 Placing into a platinum crucible for sealing;
d. placing the platinum crucible in the step c into a crucible descending furnace, heating to 400 ℃ at the speed of 15 ℃/h, preserving heat for 5 days, and then heating at the speed of 2mm/hSlowly lowering the platinum crucible, slowly cooling at a speed of 2 ℃/h, after the growth is finished, lowering the temperature of the growth furnace to 30 ℃, and taking out the platinum crucible to obtain the (NH) with the size of phi 11mm multiplied by 12mm multiplied by 4mm 4 ) 3 B 11 PO 19 F 3 Nonlinear optical crystal.
Example 22
Growth by crucible descent method (NH) 4 ) 3 B 11 PO 19 F 3 A crystal:
a. will contain NH 4 The compound being NH 4 PF 6 And NH 4 HCO 3 The B-containing compound being H 3 BO 3 The P-containing compound being NH 4 PF 6 The F-containing compound being NH 4 PF 6 In mole ratio of NH 4 Mixing the materials uniformly in a ratio of (B) to (P) and (F=7:24:2:12), sealing in a quartz tube, placing in a muffle furnace, heating to 380 ℃ at a speed of 20 ℃/h, keeping the temperature for 5 days, then cooling to 30 ℃ at a speed of 2 ℃/h, and opening the quartz tube to obtain the compound (NH) 4 ) 3 B 11 PO 19 F 3 ;
b. The compound (NH) to be obtained in step a 4 ) 3 B 11 PO 19 F 3 Sealing in quartz tube, heating to 400 deg.c at 10 deg.c/hr in muffle furnace, maintaining the temperature for 5 days, and cooling to 30 deg.c at 2 deg.c/hr; opening the high-pressure hydrothermal kettle to obtain (NH) 4 ) 3 B 11 PO 19 F 3 Seed crystal of the crystal;
c. subjecting the mixture obtained in step b (NH 4 ) 3 B 11 PO 19 F 3 Seed crystals are placed at the bottom of the quartz tube, and then the compound (NH) 4 ) 3 B 11 PO 19 F 3 Placing the mixture into a quartz tube for sealing;
d. c, placing the quartz tube in the step c in a crucible descending furnace, heating to 460 ℃ at the speed of 20 ℃/h, preserving heat for 1 day, slowly reducing the platinum crucible at the speed of 0.5mm/h, slowly reducing the temperature at the speed of 2 ℃/h, after the growth is finished, reducing the temperature of the growth furnace to 30 ℃, taking out the platinum crucible, and obtaining the rulerThe dimensions were phi 11mm by 10mm by 3mm (NH 4 ) 3 B 11 PO 19 F 3 Nonlinear optical crystal.
Example 23
Growth by crucible descent method (NH) 4 ) 3 B 11 PO 19 F 3 A crystal:
a. will contain NH 4 The compound being NH 4 PF 6 And (NH) 4 ) 2 CO 3 The compound containing B is B 2 O 3 The P-containing compound being NH 4 PF 6 The F-containing compound being NH 4 PF 6 In mole ratio of NH 4 Mixing the materials uniformly in a ratio of (B) to (P) and (F=3:11:1:6), sealing in a high-pressure hydrothermal kettle, placing in a drying oven, heating to 460 ℃ at a speed of 17 ℃/h, keeping the temperature for 2 days, then cooling to 30 ℃ at a speed of 1.5 ℃/h, and opening the high-pressure hydrothermal kettle to obtain the compound (NH) 4 ) 3 B 11 PO 19 F 3 ;
b. The compound (NH) obtained in step a 4 ) 3 B 11 PO 19 F 3 Sealing in quartz tube, heating to 500deg.C at 18 deg.C/h, maintaining for 1 day, cooling to 30deg.C at 0.5 deg.C/h, and opening quartz tube to obtain (NH) 4 ) 3 B 11 PO 19 F 3 Seed crystal of the crystal;
c. subjecting the mixture obtained in step b (NH 4 ) 3 B 11 PO 19 F 3 Seed crystals are placed at the bottom of the quartz tube, and then the compound (NH) 4 ) 3 B 11 PO 19 F 3 Placing the mixture into a quartz tube for sealing;
d. placing the quartz tube in the step c in a crucible descending furnace, heating to 400 ℃ at the speed of 10 ℃/h, preserving heat for 5 days, slowly reducing the quartz tube at the speed of 2mm/h while keeping the growth temperature unchanged, reducing the temperature of the growth furnace to 30 ℃ after the growth is finished, and taking out the quartz tube to obtain the (NH) with the size of phi 14mm multiplied by 13mm multiplied by 5mm 4 ) 3 B 11 PO 19 F 3 Nonlinear optical crystal.
Example 24
Growth by crucible descent method (NH) 4 ) 3 B 11 PO 19 F 3 A crystal:
a. will contain NH 4 The compound being NH 4 PF 6 And NH 4 HCO 3 The B-containing compound being H 3 BO 3 The P-containing compound being NH 4 PF 6 The F-containing compound being NH 4 PF 6 In mole ratio of NH 4 Mixing the materials uniformly with ratio of B, P, F=7:24:2:12, sealing in a quartz tube, placing in a muffle furnace, heating to 450deg.C at 15 ℃/h, keeping constant temperature for 3 days, cooling to 30deg.C at 1 ℃/h, and opening the quartz tube to obtain the compound (NH) 4 ) 3 B 11 PO 19 F 3 ;
b. The compound (NH) to be obtained in step a 4 ) 3 B 11 PO 19 F 3 Sealing in quartz tube, heating to 420 deg.C at a rate of 1deg.C/h in a muffle furnace, maintaining the temperature for 3 days, cooling to 30 deg.C at a rate of 1deg.C/h, and opening the quartz tube to obtain (NH) 4 ) 3 B 11 PO 19 F 3 Seed crystal of the crystal;
c. subjecting the mixture obtained in step b (NH 4 ) 3 B 11 PO 19 F 3 Seed crystals are placed at the bottom of the quartz tube, and then the compound (NH) 4 ) 3 B 11 PO 19 F 3 Placing the mixture into a quartz tube for sealing;
d. placing the quartz tube in the step c in a crucible descending furnace, heating to 500 ℃ at the speed of 14 ℃/h, preserving heat for 1 day, slowly reducing the quartz tube at the speed of 0.5mm/h while keeping the growth temperature unchanged, reducing the temperature of the growth furnace to 30 ℃ after the growth is finished, and taking out the quartz tube to obtain the (NH) with the size of phi 11mm multiplied by 13mm multiplied by 4mm 4 ) 3 B 11 PO 19 F 3 Nonlinear optical crystal.
Example 25
Growth by crucible descent method (NH) 4 ) 3 B 11 PO 19 F 3 A crystal:
a. will contain NH 4 The compound being NH 4 PF 6 And (NH) 4 ) 2 CO 3 The compound containing B is B 2 O 3 The P-containing compound being NH 4 PF 6 The F-containing compound being NH 4 PF 6 In mole ratio of NH 4 Mixing the materials uniformly with the ratio of B, P and F=3:12:1:6, filling the mixture into a high-pressure hydrothermal kettle, sealing the kettle, placing the kettle into a drying oven, heating the kettle to 500 ℃ at the speed of 10 ℃/h, keeping the temperature for 1 day, then reducing the kettle to 30 ℃ at the speed of 0.5 ℃/h, and opening the high-pressure hydrothermal kettle to obtain the compound (NH) 4 ) 3 B 11 PO 19 F 3 ;
b. The compound (NH) obtained in step a 4 ) 3 B 11 PO 19 F 3 Sealing in quartz tube, heating to 500deg.C at 20deg.C/h in muffle furnace, maintaining for 4 days, cooling to 30deg.C at 0.5deg.C/h, and opening quartz tube to obtain (NH) 4 ) 3 B 11 PO 19 F 3 Seed crystal of the crystal;
c. subjecting the mixture obtained in step b (NH 4 ) 3 B 11 PO 19 F 3 Seed crystals are placed at the bottom of the quartz tube, and then the compound (NH) 4 ) 3 B 11 PO 19 F 3 Placing the mixture into a quartz tube for sealing;
d. placing the quartz tube in the step c in a crucible descending furnace, heating to 460 ℃ at the speed of 16 ℃/h, preserving heat for 2 days, slowly reducing the quartz tube at the speed of 1mm/h, slowly reducing the temperature at the speed of 1.5 ℃/h, reducing the temperature of the growing furnace to 30 ℃ after the growth is finished, and taking out the quartz tube to obtain the (NH) with the size of phi 13mm multiplied by 12mm multiplied by 5mm 4 ) 3 B 11 PO 19 F 3 Nonlinear optical crystal.
Example 26
Growth by crucible descent method (NH) 4 ) 3 B 11 PO 19 F 3 A crystal:
a. will contain NH 4 The compound being NH 4 PF 6 And NH 4 HCO 3 The B-containing compound being H 3 BO 3 The P-containing compound being NH 4 PF 6 The F-containing compound being NH 4 PF 6 In mole ratio of NH 4 Mixing the materials uniformly in a ratio of (B) to (P) and (F=7:24:2:12), sealing in a quartz tube, placing in a muffle furnace, heating to 380 ℃ at a speed of 20 ℃/h, keeping the temperature for 5 days, then cooling to 30 ℃ at a speed of 2 ℃/h, and opening the quartz tube to obtain the compound (NH) 4 ) 3 B 11 PO 19 F 3 ;
b. The compound (NH) obtained in step a 4 ) 3 B 11 PO 19 F 3 Sealing in quartz tube, heating to 150deg.C at 15 deg.C/h in muffle furnace, maintaining for 2 days, cooling to 30deg.C at 1 deg.C/h, and opening quartz tube to obtain (NH) 4 ) 3 B 11 PO 19 F 3 Seed crystal of the crystal;
c. subjecting the mixture obtained in step b (NH 4 ) 3 B 11 PO 19 F 3 Seed crystals are placed at the bottom of the quartz tube, and then the compound (NH) 4 ) 3 B 11 PO 19 F 3 Placing the mixture into a quartz tube for sealing;
d. placing the quartz tube in the step c in a crucible descending furnace, heating to 470 ℃ at the speed of 20 ℃/h, preserving heat for 2 days, slowly reducing the quartz tube at the speed of 1mm/h, slowly reducing the temperature at the speed of 0.5 ℃/h, after the growth is finished, reducing the temperature of the growing furnace to 30 ℃, and taking out the quartz tube to obtain the (NH) with the size of phi 11mm multiplied by 13mm multiplied by 4mm 4 ) 3 B 11 PO 19 F 3 Nonlinear optical crystal.
Example 27
Growth by crucible descent method (NH) 4 ) 3 B 11 PO 19 F 3 A crystal:
a. will contain NH 4 The compound being NH 4 PF 6 And (NH) 4 ) 2 CO 3 The compound containing B is B 2 O 3 The P-containing compound being NH 4 PF 6 The F-containing compound being NH 4 PF 6 In mole ratio of NH 4 ∶B∶Mixing the materials uniformly in a ratio of P to F=3:11:1:6, sealing in a high-pressure hydrothermal kettle, placing in a drying oven, heating to 480 ℃ at a speed of 18 ℃/h, keeping the temperature for 2 days, then cooling to 30 ℃ at a speed of 1.5 ℃/h, and opening the high-pressure hydrothermal kettle to obtain the compound (NH) 4 ) 3 B 11 PO 19 F 3 ;
b. The compound (NH) obtained in step a 4 ) 3 B 11 PO 19 F 3 Sealing in quartz tube, heating to 500deg.C at the rate of 14deg.C/h in muffle furnace, maintaining the temperature for 1 day, cooling to 30deg.C at the rate of 0.5deg.C/h, and opening quartz tube to obtain (NH) 4 ) 3 B 11 PO 19 F 3 Seed crystal of the crystal;
c. step b is followed by step b to obtain (NH 4 ) 3 B 11 PO 19 F 3 Seed crystals are placed at the bottom of the quartz tube, and then the compound (NH) 4 ) 3 B 11 PO 19 F 3 Placing the mixture into a quartz tube for sealing;
d. placing the quartz tube in the step c into a crucible descending furnace, heating to 400 ℃ at the speed of 15 ℃/h, preserving heat for 3 days, slowly reducing the quartz tube at the speed of 1mm/h, slowly reducing the temperature at the speed of 1 ℃/h, after the growth is finished, reducing the temperature of the growing furnace to 30 ℃, and taking out the quartz tube to obtain the (NH) with the size of phi 11mm multiplied by 12mm multiplied by 4mm 4 ) 3 B 11 PO 19 F 3 Nonlinear optical crystal.
Example 28
Growth by crucible descent method (NH) 4 ) 3 B 11 PO 19 F 3 A crystal:
a. will contain NH 4 The compound being NH 4 PF 6 And NH 4 HCO 3 The B-containing compound being H 3 BO 3 The P-containing compound being NH 4 PF 6 The F-containing compound being NH 4 PF 6 In mole ratio of NH 4 Mixing the materials uniformly in a ratio of (B) to (P: F=7:24:2:12), sealing in a quartz tube, heating to 450deg.C at 15 ℃/h, keeping the temperature for 3 days, and adding the materials at 1 °Ch, the speed of the catalyst is reduced to 30 ℃, and the quartz tube is opened to obtain the compound (NH) 4 ) 3 B 11 PO 19 F 3 ;
b. The compound (NH) obtained in step a 4 ) 3 B 11 PO 19 F 3 Sealing in quartz tube, heating to 450deg.C at 10deg.C/h, maintaining for 3 days, cooling to 30deg.C at 1.5deg.C/h, and opening quartz tube to obtain (NH) 4 ) 3 B 11 PO 19 F 3 Seed crystal of the crystal;
c. subjecting the mixture obtained in step b (NH 4 ) 3 B 11 PO 19 F 3 Seed crystals are placed at the bottom of the quartz tube, and then the compound (NH) 4 ) 3 B 11 PO 19 F 3 Placing the mixture into a quartz tube for sealing;
d. placing the quartz tube in the step c in a crucible descending furnace, heating to 480 ℃ at the speed of 20 ℃/h, preserving heat for 1 day, slowly reducing the quartz tube at the speed of 1.5mm/h, slowly reducing the temperature at the speed of 1 ℃/h, after the growth is finished, reducing the temperature of the growing furnace to 30 ℃, and taking out the quartz tube to obtain the (NH) with the size of phi 11mm multiplied by 10mm multiplied by 4mm 4 ) 3 B 11 PO 19 F 3 Nonlinear optical crystal.
Example 29
Any of examples 13 to 28 (NH 4 ) 3 B 11 PO 19 F 3 The crystal is processed in the matching direction, and is arranged at the position 3 shown in figure 3, at room temperature, a YAG laser with the tuning QNd is used as a light source, the incident wavelength is 1064nm, and an infrared beam 2 with the wavelength of 1064nm is emitted by a YAG laser 1 with the tuning QNd to enter (NH) 4 ) 3 B 11 PO 19 F 3 And the crystal 3 generates green frequency multiplication light with the wavelength of 532nm, and the output intensity is about 1.2 times of that of the KDP with the same condition.
Example 30
Any of examples 13 to 28 (NH 4 ) 3 B 11 PO 19 F 3 The crystals were processed in the matching direction as shown in figure 3Is arranged at the position of 3, and at room temperature, a modulated QNd YAG laser is used as a light source, the incident wavelength is 532nm, and a green light beam 2 with the wavelength of 532nm is emitted by a modulated Q Nd YAG laser 1 to be injected (NH) 4 ) 3 B 11 PO 19 F 3 And the crystal 3 generates frequency multiplication light with the wavelength of 266nm, and the output intensity is about 0.2 times of that of BBO under the same condition.
Claims (8)
1. A compound ammonium borofluoride phosphate is characterized in that the chemical formula of the compound is (NH) 4 ) 3 B 11 PO 19 F 3 The molecular weight is 565.01, and the preparation method is solid phase method.
2. The preparation method of the compound ammonium borofluoride phosphate according to claim 1, which is characterized by adopting a solid phase reaction method, and comprises the following specific operations:
in mole ratio of NH 4 B: P: F=3-7:12-24:1-2:6-12 will contain NH 4 The compound being NH 4 PF 6 And (NH) 4 ) 2 CO 3 Or NH 4 PF 6 And NH 4 HCO 3 The B-containing compound being H 3 BO 3 Or B is a 2 O 3 The P-containing compound being NH 4 PF 6 The F-containing compound being NH 4 PF 6 Mixing, sealing in a high-pressure hydrothermal kettle or quartz tube, heating to 380-500deg.C at a rate of 10-20deg.C/h, maintaining for 1-5 days, cooling to 30deg.C at a rate of 0.5-2deg.C/h, and opening the kettle or quartz tube to obtain compound (NH) 4 ) 3 B 11 PO 19 F 3 。
3. A non-linear optical crystal of ammonium borophosphate fluoride is characterized by that its chemical formula is (NH) 4 ) 3 B 11 PO 19 F 3 The molecular weight is 565.01, the crystal belongs to a trigonal system, and the space group isR3, unit cell parameters area=b=11.3782(17)Å,c=11.912(3)Å, Z=3,α=β=90°,γ=120°,V=1335.6(5)Å 3 。
4. A method for producing a nonlinear optical crystal of ammonium borophosphate fluoride according to claim 3, characterized by using a flux method or a crucible lowering method:
the method adopts a fluxing agent method to grow crystals, and comprises the following steps:
a. in mole ratio of NH 4 B: P: F=3-7:12-24:1-2:6-12 will contain NH 4 The compound being NH 4 PF 6 And (NH) 4 ) 2 CO 3 Or NH 4 PF 6 And NH 4 HCO 3 The B-containing compound being H 3 BO 3 Or B is a 2 O 3 The P-containing compound being NH 4 PF 6 The F-containing compound being NH 4 PF 6 Mixing, sealing in a high-pressure hydrothermal kettle or quartz tube, heating to 380-500deg.C at a rate of 10-20deg.C/h, maintaining for 1-5 days, cooling to 30deg.C at a rate of 0.5-2deg.C/h, and opening the kettle or quartz tube to obtain compound (NH) 4 ) 3 B 11 PO 19 F 3 ;
b. The compound (NH) obtained in step a 4 ) 3 B 11 PO 19 F 3 Sealing in a high-pressure hydrothermal kettle or quartz tube, heating to 400-500deg.C at a rate of 10-20deg.C/h, keeping for 1-5 days, cooling to 30deg.C at a rate of 0.5-2deg.C/h, and opening the kettle or quartz tube to obtain (NH) 4 ) 3 B 11 PO 19 F 3 Seed crystal of the crystal;
c. placing the seed crystal obtained in step b at the bottom of a high-pressure hydrothermal kettle or quartz tube, and then placing the compound (NH) 4 ) 3 B 11 PO 19 F 3 With fluxing agent NH 4 PF 6 、NH 4 HCO 3 And B 2 O 3 Mixing, sealing in high-pressure hydrothermal kettle or quartz tube, wherein the fluxing agent NH 4 PF 6 、NH 4 HCO 3 And B 2 O 3 Molar of (2)The ratio is 1:2:6;
d. c, placing the high-pressure hydrothermal kettle or the quartz tube in the step c in a muffle furnace or a drying oven, heating to 400-500 ℃ at the speed of 10-20 ℃/h, keeping the temperature for 1-5 days, slowly cooling to 30 ℃ at the speed of 0.5-2 ℃/h, and opening the high-pressure hydrothermal kettle or the quartz tube to obtain centimeter-level (NH) 4 ) 3 B 11 PO 19 F 3 A nonlinear optical crystal;
the crystal is grown by adopting a crucible descent method, and the specific operation comprises the following steps:
a. in mole ratio of NH 4 B: P: F=3-7:12-24:1-2:6-12 will contain NH 4 The compound being NH 4 PF 6 And (NH) 4 ) 2 CO 3 Or NH 4 PF 6 And NH 4 HCO 3 The B-containing compound being H 3 BO 3 Or B is a 2 O 3 The P-containing compound being NH 4 PF 6 The F-containing compound being NH 4 PF 6 Mixing, sealing in a high-pressure hydrothermal kettle or quartz tube, heating to 380-500deg.C at a rate of 10-20deg.C/h, maintaining for 1-5 days, cooling to 30deg.C at a rate of 0.5-2deg.C/h, and opening the kettle or quartz tube to obtain compound (NH) 4 ) 3 B 11 PO 19 F 3 ;
b. The compound (NH) obtained in step a 4 ) 3 B 11 PO 19 F 3 Sealing in a high-pressure hydrothermal kettle or quartz tube, heating to 400-500deg.C at a rate of 10-20deg.C/h, keeping for 1-5 days, cooling to 30deg.C at a rate of 0.5-2deg.C/h, and opening the kettle or quartz tube to obtain (NH) 4 ) 3 B 11 PO 19 F 3 Seed crystal of the crystal;
c. placing the seed crystal obtained in step b at the bottom of a platinum crucible or quartz tube, and then placing the compound (NH) obtained in step a 4 ) 3 B 11 PO 19 F 3 Placing into a platinum crucible or a quartz tube for sealing;
d. placing the platinum crucible or quartz tube in step c into a crucible lowering furnaceHeating to 400-500 ℃ at a speed of 10-20 ℃/h, keeping the temperature for 1-5 days, and slowly reducing the platinum crucible or the quartz tube at a speed of 0.5-2 mm/h; simultaneously, keeping the growth temperature unchanged or slowly reducing the temperature at the speed of 0.5-2 ℃/h, after the growth is finished, reducing the temperature of a growth furnace to 30 ℃, and opening a platinum crucible or a quartz tube to obtain the centimeter-level (NH) 4 ) 3 B 11 PO 19 F 3 Nonlinear optical crystal.
5. Use of the ammonium borophosphate fluoride nonlinear optical crystal in accordance with claim 3 for producing multiband frequency doubling devices.
6. The use of the ammonium borophosphate fluoride nonlinear optical crystal according to claim 3 for preparing harmonic light output of 2 times or 3 times or 4 times or 5 times of 1064nm fundamental light output by a Nd-YAG laser.
7. Use of the ammonium borophosphate fluoride nonlinear optical crystal according to claim 3 for preparing deep ultraviolet frequency doubling light output below 200 nm.
8. Use of the ammonium borophosphate fluoride nonlinear optical crystal according to claim 3 for the preparation of a frequency doubling generator, an up or down frequency converter or an optical parametric oscillator.
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CN106011994A (en) * | 2016-07-26 | 2016-10-12 | 厦门大学 | Deep-ultraviolet-band nonlinear optical potassium fluoroborophosphate crystal and preparation method and application thereof |
CN106745022A (en) * | 2016-12-09 | 2017-05-31 | 中国科学院新疆理化技术研究所 | Compound ammonium fluoroborate and ammonium fluoroborate nonlinear optical crystal and preparation method and purposes |
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CN106011994A (en) * | 2016-07-26 | 2016-10-12 | 厦门大学 | Deep-ultraviolet-band nonlinear optical potassium fluoroborophosphate crystal and preparation method and application thereof |
CN106745022A (en) * | 2016-12-09 | 2017-05-31 | 中国科学院新疆理化技术研究所 | Compound ammonium fluoroborate and ammonium fluoroborate nonlinear optical crystal and preparation method and purposes |
Non-Patent Citations (1)
Title |
---|
"Fluoroborophosphates: a family of potential deep ultraviolet NLO materials";wu baolin等;《INORGANIC CHEMISTRY FRONTIERS》;第6卷(第3期);第723-730页 * |
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