CN111334858A - Compound barium fluoborate, barium fluoborate nonlinear optical crystal, preparation method and application - Google Patents

Compound barium fluoborate, barium fluoborate nonlinear optical crystal, preparation method and application Download PDF

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CN111334858A
CN111334858A CN202010150933.4A CN202010150933A CN111334858A CN 111334858 A CN111334858 A CN 111334858A CN 202010150933 A CN202010150933 A CN 202010150933A CN 111334858 A CN111334858 A CN 111334858A
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CN111334858B (en
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潘世烈
刘开通
韩健
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Xinjiang Technical Institute of Physics and Chemistry of CAS
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Xinjiang Technical Institute of Physics and Chemistry of CAS
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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
    • 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
    • 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
    • C30B17/00—Single-crystal growth onto a seed which remains in the melt during growth, e.g. Nacken-Kyropoulos 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
    • 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

Abstract

The invention relates to a compound barium fluoborate, a barium fluoborate nonlinear optical crystal, a preparation method and application thereof, wherein the chemical formula of the compound is BaBOF3Molecular weight is 221.15, and the preparation method is solid phase synthesis method or vacuum packaging method; the chemical formula of the crystal is BaBOF3Molecular weight of 221.15, belonging to monoclinic system, space group ofP21Cell parameter ofa=4.6145(17)Å，b=4.3671(16)Å，c=7.905(3)Å，β=105.519(6) ° unit cell volume 153.49(10) Å3The powder frequency doubling effect of the crystal is about KH2PO4(KDP) is 1.0 time of that of the total solid laser, the ultraviolet absorption edge is shorter than 190 nm, the crystal is grown by adopting a melt method, a high-temperature melt method, a vacuum packaging method, a hydrothermal method or a room-temperature solution method, the chemical stability of the crystal is good, and the crystal can be used as an ultraviolet and deep ultraviolet nonlinear optical crystal to be applied to an all-solid-state laser.

Description

Compound barium fluoborate, barium fluoborate nonlinear optical crystal, preparation method and application
Technical Field
The invention relates to a compound barium fluoborate BaBOF3And barium fluoroborate BaBOF3Nonlinear optical crystal and its preparation method and application.
Background
Because of the ability to produce coherent UV or DUV light, scientists have invented some NLO crystals in the UV and DUV bands, including β -BaB2O4(BBO)，LiB3O5(LBO)，CsB3O5(CBO)，CsLiB6O10(CLBO)，KBe2BO3F2(KBBF)，K3B6O10Cl (KBOC), etc. As is known, the only practical deep ultraviolet nonlinear optical crystal at present is the (KBBF) crystal invented by Chinese scientists, and the crystal has a layered growth habit, is difficult to grow large-size crystals and limits the application to a certain extent. Scientists in various countries still pay great attention to the exploration and research of various novel nonlinear optical crystals, not only pay attention to the optical performance and mechanical performance of the crystals, but also pay more and more attention to the preparation characteristics of the crystals.
In the previous researches, the invention discloses a compound barium fluoborate nonlinear optical crystal and a preparation method and application thereof (patent application No. 201010231415.1), a compound barium fluoborate and a barium fluoborate nonlinear optical crystal and a preparation method and application thereof (patent application No. 201110258171.0), and a compound ammonium fluoborate NH4B4O6F and ammonium fluoroborate NH4B4O6F nonlinear optical crystal (patent application No. 201611128283.3), compound rubidium fluoroborate and rubidium fluoroborate nonlinear optical crystal and preparation method and application (patent application No. 201710215347.1), compound cesium fluoroborate and cesium fluoroborate nonlinear optical crystal and preparation method and application (patent application No. 201710215337.8), compound sodium fluoroborate and sodium fluoroborate birefringent crystal and preparation method and applicationPreparation method and application (patent application No. 201610932882.4), compound cesium rubidium fluoroborate and cesium rubidium fluoroborate nonlinear optical crystal and preparation method and application (patent application No. 201710845438.3), and compound cesium potassium fluoroborate and cesium potassium fluoroborate nonlinear optical crystal and preparation method and application (patent application No. 201710845730.5) seven related patents. The main difference between the present invention and the seven patents is that barium fluoborate BaBOF3The medium Ba ion is connected with the boron-oxygen fluorine anion framework by a Ba-F ionic bond, the bonding force of the structure is different, the structure and the growth habit are completely different, and the barium fluoborate BaBOF3The crystal can grow in a closed system or an open system stably, and the key parameters and the crystal performance of the growth process are different from those of the first six crystals. Specifically, the present invention is clearly different from the former barium fluoroborate (patent application No. 201010231415.1 and patent application No. 201110258171.0) in structure. The molecular formula of the barium fluoborate with the patent application number of 201010231415.1 is Ba4B11O20F, molecular weight 1007.27, crystal belonging to orthorhombic system, space group Cmc21Cell parameter of
Figure BDA0002402419710000011
Unit cell volume of
Figure BDA0002402419710000012
The molecular formula of the barium fluoborate with the patent application number of 201110258171.0 is Ba3B6O11F2Molecular weight 690.88, crystal belonging to monoclinic system, space group P21Cell parameter of
Figure BDA0002402419710000013
β is 101.351(4) ° with unit cell volume of
Figure BDA0002402419710000014
The barium fluoroborate of the above two examples is a completely different compound from the barium fluoroborate of the present invention.
Disclosure of Invention
The object of the present invention is to provideA compound barium fluoborate, the chemical formula of which is BaBOF3Molecular weight is 221.15, and the preparation method is solid phase reaction or vacuum packaging.
Another object of the present invention is to provide barium fluoroborate BaBOF3A nonlinear optical crystal of the formula BaBOF3And the molecular weight is 221.15. The crystal structure belongs to a monoclinic system, and the space group is P21Cell parameter of
Figure BDA0002402419710000022
Figure BDA0002402419710000021
β is 105.519(6) ° with unit cell volume of
Figure BDA0002402419710000023
It is a further object of the present invention to provide barium fluoroborate BaBOF3The preparation method of the nonlinear optical crystal adopts a melt method, a high-temperature melt method, a vacuum packaging method, a hydrothermal method or a room-temperature solution method to grow the crystal.
It is still another object of the present invention to provide barium fluoroborate BaBOF3Use of a nonlinear optical crystal.
The chemical formula of the compound barium fluoborate is BaBOF3Molecular weight is 221.15, and the preparation method is solid phase synthesis method or vacuum packaging method.
The preparation method of the compound barium fluoborate adopts a solid-phase synthesis method or a vacuum packaging method, and comprises the following specific operations:
the solid phase synthesis method is used for preparing a compound barium fluoborate:
uniformly mixing a Ba-containing compound, a B-containing compound and a F-containing compound according to the molar ratio of Ba to B to F of 1 to 3, putting the mixture into a platinum crucible, placing the platinum crucible into a muffle furnace, heating the mixture to 310-650 ℃, and keeping the temperature for 24-120 hours to obtain a compound BaBOF3The Ba-containing compound is BaF2、Ba(OH)2、BaCO3、Ba(NO3)2、Ba(HCO3)2Or Ba (BF)4)2(ii) a The compound containing B is H3BO3、B2O3、Ba(BF4)2(ii) a The F-containing compound is BaF2Or Ba (BF)4)2；
The vacuum packaging method is used for preparing a compound barium fluoborate:
uniformly mixing Ba-containing compound, B-containing compound and F-containing compound according to a molar ratio of Ba to B to F of 1 to 5 to 3, putting the mixture into a quartz tube, vacuumizing the quartz tube until the vacuum degree reaches 1 × 10-3Pa, sealing at high temperature, placing in a muffle furnace, heating to 310-650 ℃ at the rate of 5-10 ℃/h, and keeping the temperature for 24-120 hours to obtain a compound BaBOF3The Ba-containing compound is BaF2、Ba(OH)2、BaCO3、Ba(NO3)2、Ba(HCO3)2Or Ba (BF)4)2(ii) a The compound containing B is H3BO3、B2O3、Ba(BF4)2(ii) a The F-containing compound is BaF2Or Ba (BF)4)2。
A barium fluoborate nonlinear optical crystal has a chemical formula of BaBOF3Molecular weight of 221.15, belonging to monoclinic system, space group of P21Cell parameter of
Figure BDA0002402419710000024
β is 105.519(6) ° with unit cell volume of
Figure BDA0002402419710000025
The preparation method of the barium fluoborate nonlinear optical crystal adopts a melt method, a high-temperature melt method, a vacuum packaging method, a hydrothermal method or a room-temperature solution method to grow the crystal;
the melt method for growing the barium fluoborate nonlinear optical crystal comprises the following specific operations:
a. uniformly mixing a Ba-containing compound, a B-containing compound and a F-containing compound according to a molar ratio of Ba to B to F of 1 to 3, putting the mixture into a platinum crucible, putting the platinum crucible into a muffle furnace, heating to 310-650 ℃, and keeping the temperature constantHeating for 24-120 hours to obtain the compound BaBOF3A polycrystalline powder, the Ba-containing compound being BaF2、Ba(OH)2、BaCO3、Ba(NO3)2、Ba(HCO3)2Or Ba (BF)4)2(ii) a The compound containing B is H3BO3、B2O3、Ba(BF4)2(ii) a The F-containing compound is BaF2Or Ba (BF)4)2；
b. B, mixing the compound BaBOF prepared in the step a3Putting the polycrystalline powder into a platinum crucible, placing the platinum crucible in a muffle furnace, heating to 550-750 ℃, and keeping the temperature for 10-120 hours to obtain a mixed melt;
c. c, slowly reducing the temperature of the mixed melt obtained in the step b to 310 ℃ at the speed of 0.1-2 ℃/h, and rapidly reducing the temperature to room temperature at the speed of 5-10 ℃/h to obtain BaBOF3Seed crystal;
d. adopting a pulling method to grow crystals in a compound melt: c, fixing the seed crystal obtained in the step c on a seed crystal rod, lowering the seed crystal from the upper part of the mixed melt prepared in the step b, applying crystal rotation of 2-20rpm through a crystal growth controller, pulling the seed crystal at the speed of 1-10 mm/day, simultaneously cooling at the speed of 0.1-10 ℃/h, and after the crystal growth stops, obtaining BaBOF3A nonlinear optical crystal;
or growing crystals in a melt of the compound by kyropoulos: c, fixing the seed crystal obtained in the step c on a seed crystal rod, lowering the seed crystal from the upper part of the melt prepared in the step b, cooling at the speed of 0.1-10 ℃/h to enable the crystal to grow for 5-15 hours, slowly lifting the crystal without deviating from the liquid level to continue to grow, repeating the steps, and obtaining BaBOF after the crystal growth is stopped3A nonlinear optical crystal;
or growing crystals in a compound melt by the Bridgman method: c, placing the seed crystal prepared in the step c at the bottom of the crucible, and then placing the compound BaBOF prepared in the step a3Placing the polycrystal into a crucible, sealing the platinum crucible, heating the growth furnace to 550-750 ℃, keeping the temperature for 10-120 hours, adjusting the position of the crucible to slightly melt the seed crystal, then reducing the crucible at the speed of 1-10 mm/day, and simultaneously keeping the growth temperature unchanged or at the maximumThe temperature reduction rate of 3 ℃/h is reduced to 350 ℃, and after the growth is finished, the temperature is rapidly reduced to the room temperature at the rate of 5-10 ℃/h, and then the BaBOF is obtained3A nonlinear optical crystal;
the high-temperature melt method for growing the barium fluoborate nonlinear optical crystal comprises the following specific operations:
a. uniformly mixing a Ba-containing compound, a B-containing compound and a F-containing compound according to the molar ratio of Ba to B to F of 1 to 3, putting the mixture into a platinum crucible, placing the platinum crucible into a muffle furnace, heating the mixture to 310-650 ℃, and keeping the temperature for 24-120 hours to obtain a compound BaBOF3A polycrystalline powder, the Ba-containing compound being BaF2、Ba(OH)2、BaCO3、Ba(NO3)2、Ba(HCO3)2Or Ba (BF)4)2(ii) a The compound containing B is H3BO3、B2O3、Ba(BF4)2(ii) a The F-containing compound is BaF2Or Ba (BF)4)2；
b. B, mixing the compound BaBOF obtained in the step a3Uniformly mixing the polycrystalline powder and the fluxing agent according to the molar ratio of 1:0.1-6, then placing the mixture into a platinum crucible, heating to 550-; the cosolvent is H3BO3、B2O3PbO or PbF2；
c. Preparing seed crystals: b, placing the mixed melt obtained in the step b into a single crystal furnace, slowly cooling to 350 ℃ at the speed of 0.1-2 ℃/h, and then rapidly cooling to room temperature at the speed of 5-10 ℃/h to obtain BaBOF3Seed crystal;
d. growing a crystal: c, fixing the seed crystal obtained in the step c on a seed crystal rod, feeding the seed crystal from the upper part of the mixed melt prepared in the step b, applying crystal rotation of 2-20rpm through a crystal growth controller, cooling at the speed of 0.1-3 ℃/h, and obtaining BaBOF after crystal growth is stopped3A nonlinear optical crystal;
the vacuum packaging method for growing the barium fluoborate nonlinear optical crystal comprises the following specific operations:
a. massaging Ba-containing compound, B-containing compound and F-containing compoundUniformly mixing Ba, B and F in a molar ratio of 1:1:3, putting the mixture into a platinum crucible, putting the platinum crucible into a muffle furnace, heating the mixture to the temperature of 310 ℃ and 650 ℃, and keeping the temperature for 24-120 hours to obtain a compound BaBOF3A polycrystalline powder, the Ba-containing compound being BaF2、Ba(OH)2、BaCO3、Ba(NO3)2、Ba(HCO3)2Or Ba (BF)4)2(ii) a The compound containing B is H3BO3、B2O3、Ba(BF4)2(ii) a The F-containing compound is BaF2Or Ba (BF)4)2；
b. B, mixing the compound BaBOF obtained in the step a3Uniformly mixing the polycrystalline powder and the fluxing agent according to the molar ratio of 0-1:0.1-6, placing the mixture into a quartz tube, placing the quartz tube into a muffle furnace after high-temperature sealing, heating to 550-3The cosolvent is H3BO3、B2O3PbO or PbF2；
The hydrothermal method for growing the barium fluoborate nonlinear optical crystal comprises the following specific operations:
a. uniformly mixing a Ba-containing compound, a B-containing compound and a F-containing compound according to the molar ratio of Ba to B to F of 1 to 3, putting the mixture into a platinum crucible, placing the platinum crucible into a muffle furnace, heating the mixture to 310-650 ℃, and keeping the temperature for 24-120 hours to obtain a compound BaBOF3A polycrystalline powder, the Ba-containing compound being BaF2、Ba(OH)2、BaCO3、Ba(NO3)2、Ba(HCO3)2Or Ba (BF)4)2(ii) a The compound containing B is H3BO3、B2O3、Ba(BF4)2(ii) a The F-containing compound is BaF2Or Ba (BF)4)2；
b. B, mixing the compound BaBOF obtained in the step a3Dissolving the polycrystalline powder in deionized water, subjecting the incompletely dissolved mixture to ultrasonic treatment at 60 deg.C to thoroughly mix and dissolve, and dissolving with HF and Ba (OH)2Adjusting the pH value to 8-11;
c. b, transferring the mixed solution obtained in the step b into a clean and pollution-free lining of a high-pressure reaction kettle with the volume of 100mL, and screwing and sealing the reaction kettle;
d. placing the high-pressure reaction kettle in a constant temperature box, heating to 150-350 ℃, keeping the temperature for 5-8 days, and then cooling to room temperature at the cooling rate of 5-20 ℃/day to obtain BaBOF3A nonlinear optical crystal;
the room temperature solution method for growing the barium fluoborate nonlinear optical crystal comprises the following specific operations:
a. uniformly mixing a Ba-containing compound, a B-containing compound and a F-containing compound according to the molar ratio of Ba to B to F of 1 to 5 to 3, putting the mixture into a platinum crucible, placing the platinum crucible into a muffle furnace, heating the mixture to 310-650 ℃, and keeping the temperature for 24 to 120 hours to obtain a compound BaBOF3A polycrystalline powder, the Ba-containing compound being BaF2、Ba(OH)2、BaCO3、Ba(NO3)2、Ba(HCO3)2Or Ba (BF)4)2(ii) a The compound containing B is H3BO3、B2O3、Ba(BF4)2(ii) a The F-containing compound is BaF2Or Ba (BF)4)2；
b. B, mixing the compound BaBOF obtained in the step a3Placing the polycrystalline powder into a clean glass container, adding 20-100mL deionized water, performing ultrasonic treatment to mix thoroughly and dissolve, and dissolving with HF and Ba (OH)2Adjusting pH to 8-11, and filtering with filter paper to obtain mixed solution;
c. b, placing the mixed solution obtained in the step b into a clean glass container, sealing the container by using weighing paper, placing the container in a static environment without shaking, pollution and air convection, pricking a plurality of small holes on the seal to adjust the evaporation rate of water in the water solution, and standing the container for 5 to 20 days at room temperature;
d. c, growing crystal particles on the bottom of the container by the solution in the step c until the size of the crystal particles is not obviously changed any more, and obtaining seed crystals;
e. selecting the seed crystal with better quality in the step d, suspending the seed crystal in the mixed solution prepared in the step b, standing and growing for 10-30 days at room temperature to obtain the seed crystalTo BaBOF3A nonlinear optical crystal.
The barium fluoborate nonlinear optical crystal is used for outputting harmonic light of 2 frequency multiplication, 3 frequency multiplication, 4 frequency multiplication and 5 frequency multiplication on 1064nm fundamental frequency light output by a Nd-YAG laser.
The application of the barium fluoborate nonlinear optical crystal in preparing the optical crystal which generates deep ultraviolet frequency doubling light output below 200 nm.
The compound barium fluoborate nonlinear optical crystal is used for preparing a frequency doubling generator, an upper or lower frequency converter or an optical parametric oscillator.
The invention relates to a preparation method of barium fluoborate nonlinear optical crystal, wherein containers used in the preparation process are a platinum crucible, an iridium crucible, a ceramic crucible, a quartz tube, a conical flask, a beaker, and a hydrothermal kettle with a polytetrafluoroethylene lining or a stainless steel lining filled with a platinum sleeve. When the container is a quartz tube, vacuumizing is needed before sealing, so that the quartz tube is prevented from being burst due to volatilization of raw materials in the reaction process. When the container is a conical bottle or a beaker, the container is cleaned by acid, rinsed by deionized water and dried.
According to the preparation method of the barium fluoborate nonlinear optical crystal, a resistance furnace used in the preparation process is a muffle furnace or a drying oven.
The BaBOF with centimeter-sized dimension is obtained by adopting the preparation method of the barium fluoborate nonlinear optical crystal3The nonlinear optical crystal BaBOF with corresponding large size can be obtained by using a large-size crucible or container and prolonging the growth period of the crystal3In the BaBOF3The crystal is easy to grow, transparent and free of package in the growth of the nonlinear optical crystal, and has the advantages of high growth speed, low cost, easy obtainment of large-size crystals and the like.
The large-size BaBOF obtained by adopting the preparation method of the barium fluoborate nonlinear optical crystal3Non-linear optical crystal, according to the crystallographic data of crystal, orienting the blank of crystal, cutting the crystal according to required angle, thickness and cross-section size, polishing the light-passing surface of crystal, i.e. polishingCan be used as a non-linear optical device, the BaBOF3The nonlinear optical crystal has the advantages of light transmission band reaching deep ultraviolet region, stable physical and chemical properties, difficult deliquescence, easy processing and storage and the like.
Drawings
FIG. 1 shows BaBOF, a compound of the present invention3The powder XRD spectrum of (1);
FIG. 2 is a BaBOF of the present invention3A structure of a crystal;
FIG. 3 is a BaBOF of the present invention3Working principle diagram of nonlinear optical device made of crystal, wherein 1 is laser, 2 is emitted light beam, and 3 is BaBOF3Crystal, 4 is emergent light beam, and 5 is filter.
Detailed Description
The present invention is further described below with reference to examples. It should be noted that the following examples are not intended to limit the scope of the present invention, and any modifications made on the basis of the present invention do not depart from the spirit of the present invention. The raw materials or equipment used in the present invention are commercially available unless otherwise specified.
Example 1
Preparation of the compound:
according to the reaction formula: 6BaF2+2B2O3→4BaBOF3+2BaO, synthesizing BaBOF compound by solid phase reaction method3：
Mixing BaF2，B2O3Uniformly mixing the raw materials according to a molar ratio of 3:1, putting the mixture into a platinum crucible, putting the platinum crucible into a muffle furnace, heating the mixture to 500 ℃, and keeping the temperature for 48 hours to obtain a compound BaBOF3The polycrystalline powder of (4).
Example 2
Preparation of the compound:
according to the reaction formula: 3Ba (BF)4)2+B2O3→3BaBOF3+5BF3Synthesizing a compound BaBOF by adopting a solid-phase reaction method3：
Mixing Ba (BF)4)2，B2O3Uniformly mixing the components according to the molar ratio of 3:1, putting the mixture into a platinum crucible, putting the platinum crucible into a muffle furnace, and heating the muffle furnace to the temperatureKeeping the temperature at 500 ℃ for 48 hours to obtain a compound BaBOF3The polycrystalline powder of (4).
Example 3
Preparation of the compound:
according to the reaction formula: 3Ba (BF)4)2+2H3BO3→3BaBOF3+BF3+3H2O, synthesizing a compound BaBOF by adopting a solid-phase reaction method3：
Mixing Ba (BF)4)2，H3BO3Uniformly mixing the raw materials according to the molar ratio of 3:2, putting the mixture into a platinum crucible, putting the platinum crucible into a muffle furnace, heating the mixture to 550 ℃, and keeping the temperature for 24 hours to obtain a compound BaBOF3The polycrystalline powder of (4).
Example 4
Preparation of the compound:
according to the reaction formula: 3BaF2+2H3BO3→2BaBOF3+BaO+3H2O, synthesizing a compound BaBOF by adopting a solid-phase reaction method3：
Mixing BaF2，H3BO3Uniformly mixing the raw materials according to the molar ratio of 3:2, putting the mixture into a platinum crucible, putting the platinum crucible into a muffle furnace, heating the mixture to 550 ℃, and keeping the temperature for 24 hours to obtain a compound BaBOF3The polycrystalline powder of (4).
Example 5
Preparation of the compound:
according to the reaction formula: ba (OH)2+3Ba(BF4)2→BaBOF3+3BaF2+5BF3+H2O, synthesizing a compound BaBOF by adopting a solid-phase reaction method3：
A general reaction of Ba (OH)2，Ba(BF4)2Uniformly mixing the raw materials according to the molar ratio of 1:3, putting the mixture into a platinum crucible, putting the platinum crucible into a muffle furnace, heating the mixture to 310 ℃, and keeping the temperature for 120 hours to obtain a compound BaBOF3The polycrystalline powder of (4).
Example 6
Preparation of the compound:
according to the reaction formula: ba (HCO)3)2+Ba(BF4)2→BaBOF3+BaF2+BF3+H2O+CO2Synthesizing a compound BaBOF by adopting a solid-phase reaction method3：
Mixing Ba (HCO)3)2，Ba(BF4)2Uniformly mixing the raw materials according to the molar ratio of 1:1, putting the mixture into a platinum crucible, putting the platinum crucible into a muffle furnace, heating the mixture to 550 ℃, and keeping the temperature for 72 hours to obtain a compound BaBOF3The polycrystalline powder of (4).
Example 7
Preparation of the compound:
according to the reaction formula: BaCO3+Ba(BF4)2→BaBOF3+BaF2+BF3+CO2Synthesizing a compound BaBOF by adopting a solid-phase reaction method3：
Mixing BaCO3，Ba(BF4)2Uniformly mixing the components according to the molar ratio of 1:1, putting the mixture into a platinum crucible, putting the platinum crucible into a muffle furnace, heating the mixture to 600 ℃, and keeping the temperature for 72 hours to obtain a compound BaBOF3The polycrystalline powder of (4).
Example 8
Preparation of the compound:
according to the reaction formula: ba (NO)3)2+Ba(BF4)2→BaBOF3+BaF2+BF3+N2O5Synthesizing a compound BaBOF by adopting a solid-phase reaction method3：
Mixing Ba (NO)3)2，Ba(BF4)2Uniformly mixing the raw materials according to the molar ratio of 1:1, putting the mixture into a platinum crucible, putting the platinum crucible into a muffle furnace, heating the mixture to 650 ℃, and keeping the temperature for 72 hours to obtain a compound BaBOF3The polycrystalline powder of (4).
Example 9
Preparation of the compound:
according to the reaction formula: 6BaF2+2B2O3→4BaBOF3+2BaO, synthesizing compound BaBOF by vacuum packaging method3：
Mixing BaF2，B2O3Mixing uniformly according to a molar ratio of 3:1, placing into a quartz tube with a diameter of 40mm, vacuumizing the quartz tube until the vacuum degree reaches 1 × 10-3Pa, sealing at high temperature, placing in a muffle furnace at 10 deg.C/hHeating to 600 ℃, keeping the temperature for 24 hours to obtain a compound BaBOF3The polycrystalline powder of (4).
Uniformly mixing Ba-containing compound, B-containing compound and F-containing compound according to a molar ratio of Ba to B to F of 1 to 5 to 3, putting the mixture into a quartz tube, vacuumizing the quartz tube until the vacuum degree reaches 1 × 10-3Pa, sealing at high temperature, placing in a muffle furnace, heating to 310-650 ℃ at the rate of 5-10 ℃/h, and keeping the temperature for 24-120 hours to obtain a compound BaBOF3The Ba-containing compound is BaF2、Ba(OH)2、BaCO3、Ba(NO3)2、Ba(HCO3)2Or Ba (BF)4)2(ii) a The compound containing B is H3BO3、B2O3、Ba(BF4)2(ii) a The F-containing compound is BaF2Or Ba (BF)4)2。
Example 10
Preparation of the compound:
according to the reaction formula: 3Ba (BF)4)2+B2O3→3BaBOF3+5BF3Synthesizing a compound BaBOF by adopting a vacuum packaging method3：
Mix 3Ba (BF)4)2，B2O3Mixing uniformly according to a molar ratio of 3:1, placing into a quartz tube with a diameter of 40mm, vacuumizing the quartz tube until the vacuum degree reaches 1 × 10-3Pa, sealing at high temperature, placing in a muffle furnace, heating to 600 ℃ at the speed of 10 ℃/h, and keeping the temperature for 24 hours to obtain a compound BaBOF3The polycrystalline powder of (4).
Example 11
Preparation of the compound:
according to the reaction formula: 3BaF2+2H3BO3→2BaBOF3+BaO+3H2O, synthesizing a compound BaBOF by adopting a vacuum packaging method3：
Mixing BaF2，H3BO3Mixing uniformly according to a molar ratio of 3:2, placing into a quartz tube with a diameter of 40mm, vacuumizing the quartz tube until the vacuum degree reaches 1 × 10-3Pa, sealing at high temperature, placing in a muffle furnace, and raising at a rate of 5 ℃/hHeating to 500 deg.C, and maintaining the temperature for 72 hr to obtain BaBOF compound3The polycrystalline powder of (4).
Example 12
Preparation of the compound:
according to the reaction formula: 3Ba (BF)4)2+2H3BO3→3BaBOF3+BF3+3H2O, synthesizing a compound BaBOF by adopting a vacuum packaging method3：
Mixing Ba (BF)4)2，H3BO3Mixing uniformly according to a molar ratio of 3:2, placing into a quartz tube with a diameter of 40mm, vacuumizing the quartz tube until the vacuum degree reaches 1 × 10-3Pa, sealing at high temperature, placing in a muffle furnace, heating to 500 ℃ at the rate of 5 ℃/h, and keeping the temperature for 72 hours to obtain a compound BaBOF3The polycrystalline powder of (4).
Example 13
Preparation of the compound:
according to the reaction formula: ba (OH)2+3Ba(BF4)2→BaBOF3+3BaF2+5BF3+H2O, synthesizing a compound BaBOF by adopting a vacuum packaging method3：
A general reaction of Ba (OH)2，Ba(BF4)2Mixing uniformly according to a molar ratio of 1:3, placing into a quartz tube with a diameter of 40mm, vacuumizing the quartz tube until the vacuum degree reaches 1 × 10-3Pa, sealing at high temperature, placing in a muffle furnace, heating to 350 ℃ at the speed of 8 ℃/h, and keeping the temperature for 72 hours to obtain a compound BaBOF3The polycrystalline powder of (4).
Example 14
Preparation of the compound:
according to the reaction formula: ba (HCO)3)2+Ba(BF4)2→BaBOF3+BaF2+BF3+H2O+CO2Synthesizing a compound BaBOF by adopting a vacuum packaging method3：
Mixing Ba (HCO)3)2，Ba(BF4)2Mixing uniformly according to a molar ratio of 1:1, placing into a quartz tube with a diameter of 40mm, vacuumizing the quartz tube until the vacuum degree reaches 1 × 10-3Pa, highSealing, heating to 600 deg.C at a rate of 5 deg.C/h, and holding for 96 hr to obtain BaBOF compound3The polycrystalline powder of (4).
Example 15
Preparation of the compound:
according to the reaction formula: BaCO3+Ba(BF4)2→BaBOF3+BaF2+BF3+CO2Synthesizing a compound BaBOF by adopting a vacuum packaging method3：
Mixing BaCO3，Ba(BF4)2Mixing uniformly according to a molar ratio of 1:1, placing into a quartz tube with a diameter of 40mm, vacuumizing the quartz tube until the vacuum degree reaches 1 × 10-3Pa, sealing at high temperature, placing in a muffle furnace, heating to 650 ℃ at the speed of 10 ℃/h, and keeping the temperature for 120 hours to obtain a compound BaBOF3The polycrystalline powder of (4).
Example 16
Preparation of the compound:
according to the reaction formula: ba (NO)3)2+Ba(BF4)2→BaBOF3+BaF2+BF3+N2O5Synthesizing a compound BaBOF by adopting a vacuum packaging method3：
Mixing Ba (NO)3)2，Ba(BF4)2Mixing uniformly according to a molar ratio of 1:1, placing into a quartz tube with a diameter of 40mm, vacuumizing the quartz tube until the vacuum degree reaches 1 × 10-3Pa, sealing at high temperature, placing in a muffle furnace, heating to 580 ℃ at the rate of 5 ℃/h, and keeping the temperature for 96 hours to obtain a compound BaBOF3The polycrystalline powder of (4).
Example 17
Preparation of the compound:
according to the reaction formula: 3Ba (BF)4)2+B2O3→3BaBOF3+5BF3Synthesizing a compound BaBOF by adopting a solid-phase reaction method3：
Mixing Ba (BF)4)2，B2O3Uniformly mixing the components according to the molar ratio of 3:1, putting the mixture into a high-pressure hydrothermal kettle, putting the kettle into a muffle furnace, heating the kettle to 350 ℃, and keeping the temperature constantHeating for 48 hours to obtain a compound BaBOF3The polycrystalline powder of (4).
Example 18
Preparation of the compound:
according to the reaction formula: 3Ba (BF)4)2+2H3BO3→3BaBOF3+BF3+3H2O, synthesizing a compound BaBOF by adopting a solid-phase reaction method3：
Mixing Ba (BF)4)2，H3BO3Uniformly mixing the raw materials according to a molar ratio of 3:2, putting the mixture into a high-pressure hydrothermal kettle, putting the kettle into a muffle furnace, heating the kettle to 350 ℃, and keeping the temperature for 24 hours to obtain a compound BaBOF3The polycrystalline powder of (4).
Example 19
Melt method for growing BaBOF3Nonlinear optical crystal:
BaBOF, a compound prepared according to example 13Putting the polycrystalline powder into a platinum crucible, placing the platinum crucible in a muffle furnace, heating to 750 ℃, and keeping the temperature for 10 hours to obtain a mixed melt;
slowly reducing the temperature of the obtained mixed melt to 310 ℃ at the speed of 0.1 ℃/h, and rapidly reducing the temperature to room temperature at the speed of 5 ℃/h to obtain BaBOF3Seed crystal;
fixing the obtained seed crystal on a seed crystal rod, putting the seed crystal from the upper part of the mixed melt containing the obtained mixed melt, applying crystal rotation of 2rpm through a crystal growth controller, pulling the seed crystal at the speed of 1 mm/day, cooling at the speed of 0.1 ℃/h, and obtaining BaBOF with the size of 10mm × 12mm × 9mm after the crystal growth stops3A nonlinear optical crystal.
Example 20
Melt method for growing BaBOF3Nonlinear optical crystal:
BaBOF, a compound prepared according to example 33Putting the polycrystalline powder into a platinum crucible, placing the platinum crucible in a muffle furnace, heating to 550 ℃, and keeping the temperature for 120 hours to obtain a mixed melt;
slowly reducing the temperature of the obtained mixed melt to 350 ℃ at the speed of 2 ℃/h, rapidly reducing the temperature to room temperature at the speed of 10 ℃/h,to obtain BaBOF3Seed crystal;
fixing the obtained seed crystal on a seed crystal rod, putting the seed crystal from the upper part of the mixed melt containing the obtained mixed melt, applying crystal rotation of 20rpm through a crystal growth controller, pulling the seed crystal at the speed of 10 mm/day, cooling at the speed of 10 ℃/h, and obtaining BaBOF with the size of 12mm × 10mm × 8mm after the crystal growth stops3A nonlinear optical crystal.
Example 21
Melt method for growing BaBOF3Nonlinear optical crystal:
BaBOF, a compound prepared according to example 23Putting the polycrystalline powder into a platinum crucible, placing the platinum crucible in a muffle furnace, heating to 700 ℃, and keeping the temperature for 100 hours to obtain a mixed melt;
slowly reducing the temperature of the obtained mixed melt to 350 ℃ at the speed of 1.5 ℃/h, and rapidly reducing the temperature to room temperature at the speed of 8 ℃/h to obtain BaBOF3Seed crystal;
fixing the obtained seed crystal on a seed crystal rod, lowering the seed crystal from the upper part of the mixed melt containing the obtained seed crystal, cooling at the speed of 0.1 ℃/h to grow the crystal for 5 hours, slowly lifting the crystal without departing from the liquid level, continuing to grow the crystal, repeating the steps for three times to obtain the BaBOF with the size of 11mm × 10mm, × 9mm and the size of 359 mm3A nonlinear optical crystal.
Example 22
Melt method for growing BaBOF3Nonlinear optical crystal:
BaBOF, a compound prepared according to example 43Putting the polycrystalline powder into a platinum crucible, placing the platinum crucible in a muffle furnace, heating to 700 ℃, and keeping the temperature for 24 hours to obtain a mixed melt;
slowly reducing the temperature of the obtained mixed melt to 350 ℃ at the speed of 1 ℃/h, and rapidly reducing the temperature to room temperature at the speed of 6 ℃/h to obtain BaBOF3Seed crystal;
growing crystals by a kyropoulos method: fixing the obtained seed crystal on a seed crystal rod, discharging the seed crystal from the upper part of the mixed melt containing the obtained seed crystal, and cooling at the speed of 10 ℃/h to ensure that the crystal grows for 15 hoursSlowly lifting the crystal without deviating from the liquid level, continuing to grow, repeating the steps for three times to obtain BaBOF with the size of 15mm × 13mm × 10mm3A nonlinear optical crystal.
Example 23
Melt method for growing BaBOF3Nonlinear optical crystal:
BaBOF, a compound prepared according to example 53Putting the polycrystalline powder into a platinum crucible, heating to 700 ℃, and keeping the temperature for 10 hours to obtain a mixed melt;
slowly reducing the temperature of the obtained mixed melt to 350 ℃ at the speed of 2 ℃/h, and rapidly reducing the temperature to room temperature at the speed of 5 ℃/h to obtain BaBOF3Seed crystal;
growing crystals in a compound melt using the Bridgman method: the resulting seed crystal was placed at the bottom of the crucible, and the compound BaBOF prepared in example 5 was added3Putting polycrystalline powder into a crucible, sealing the platinum crucible, heating the growth furnace to 750 ℃, keeping the temperature for 10 hours, adjusting the position of the crucible to slightly melt the seed crystal, then reducing the crucible at a speed of 1 mm/day, reducing the temperature to 350 ℃ at a cooling rate of 3 ℃/h, and after the growth is finished, rapidly reducing the temperature to room temperature at a rate of 10 ℃/h to obtain BaBOF with the size of 13mm × 11mm, × 10mm3A nonlinear optical crystal.
Example 24
Melt method for growing BaBOF3Nonlinear optical crystal:
BaBOF, a compound prepared according to example 63Putting the polycrystalline powder into a platinum crucible, heating to 730 ℃, and keeping the temperature for 60 hours to obtain a mixed melt;
slowly reducing the temperature of the obtained mixed melt to 350 ℃ at the speed of 1.5 ℃/h, and rapidly reducing the temperature to room temperature at the speed of 5 ℃/h to obtain BaBOF3Seed crystal;
growing crystals in a compound melt using the Bridgman method: the resulting seed crystal was placed at the bottom of the crucible, and the compound BaBOF prepared in example 6 was added3Putting the polycrystalline powder into a crucible, sealing the platinum crucible, heating the growth furnace to 550 ℃, keeping the temperature for 120 hours, and adjusting the position of the crucible to ensure that the seed crystal is positionedMicro-melting, then reducing the crucible at the speed of 10 mm/day, simultaneously keeping the growth temperature unchanged, and after the growth is finished, rapidly reducing the temperature to room temperature at the speed of 10 ℃/h to obtain BaBOF with the size of 11mm × 10mm, × 9mm3A nonlinear optical crystal.
Example 25
High-temperature melt method for growing BaBOF3Nonlinear optical crystal:
BaBOF, a compound prepared according to example 83Polycrystalline powder and flux B2O3Uniformly mixing the components according to the molar ratio of 1:0.1, putting the mixture into a platinum crucible, heating the mixture to 750 ℃, and keeping the temperature for 5 hours to obtain a mixed solution;
preparing seed crystals: placing the obtained mixed melt in a single crystal furnace, slowly reducing the temperature to 350 ℃ at the speed of 0.1 ℃/h, and rapidly reducing the temperature to room temperature at the speed of 5 ℃/h to obtain BaBOF3Seed crystal;
fixing the obtained seed crystal on a seed crystal rod, dropping the seed crystal from the upper part of the seed crystal containing the prepared mixed melt, applying crystal rotation of 2rpm through a crystal growth controller, cooling at the speed of 0.1 ℃/h, and obtaining BaBOF with the size of 12mm × 10mm, × 8mm after the crystal growth is stopped3A nonlinear optical crystal.
Example 26
High-temperature melt method for growing BaBOF3Nonlinear optical crystal:
BaBOF, a compound obtained according to example 93Polycrystalline powder and flux H3BO3Uniformly mixing the components according to the molar ratio of 1:6, putting the mixture into a platinum crucible, heating the mixture to 730 ℃, and keeping the temperature for 52 hours to obtain a mixed solution;
preparing seed crystals: placing the obtained mixed melt in a single crystal furnace, slowly cooling to 350 ℃ at the speed of 1 ℃/h, and then rapidly cooling to room temperature at the speed of 8 ℃/h to obtain BaBOF3Seed crystal;
growing a crystal: fixing the obtained seed crystal on a seed crystal rod, discharging the seed crystal from the upper part of the seed crystal containing the prepared mixed melt, applying crystal rotation of 10rpm through a crystal growth controller, cooling at the speed of 1 ℃/h, and stopping crystal growthThen obtaining BaBOF with the size of 12mm × 11mm × 10mm3A nonlinear optical crystal.
Example 27
High-temperature melt method for growing BaBOF3Nonlinear optical crystal:
BaBOF, a compound prepared according to example 103Uniformly mixing the polycrystalline powder and a fluxing agent PbO according to a molar ratio of 1:4, putting the mixture into a platinum crucible, heating to 600 ℃, and keeping the temperature for 5 hours to obtain a mixed solution;
preparing seed crystals: placing the obtained mixed melt in a single crystal furnace, slowly reducing the temperature to 350 ℃ at the speed of 1.5 ℃/h, and rapidly reducing the temperature to room temperature at the speed of 10 ℃/h to obtain BaBOF3Seed crystal;
fixing the obtained seed crystal on a seed crystal rod, dropping the seed crystal from the upper part of the seed crystal containing the prepared mixed melt, applying crystal rotation of 10rpm through a crystal growth controller, cooling at the speed of 1 ℃/h, and obtaining BaBOF with the size of 11mm × 11mm, × 10mm after the crystal growth is stopped3A nonlinear optical crystal.
Example 28
High-temperature melt method for growing BaBOF3Nonlinear optical crystal:
BaBOF, a compound obtained according to example 113Polycrystalline powder and flux PbF2Uniformly mixing the components according to the molar ratio of 1:3, putting the mixture into a platinum crucible, heating the mixture to 600 ℃, and keeping the temperature for 120 hours to obtain mixed melt;
preparing seed crystals: placing the obtained mixed melt in a single crystal furnace, slowly reducing the temperature to 350 ℃ at the speed of 2 ℃/h, and rapidly reducing the temperature to room temperature at the speed of 10 ℃/h to obtain BaBOF3Seed crystal;
fixing the obtained seed crystal on a seed crystal rod, dropping the seed crystal from the upper part of the seed crystal containing the prepared mixed melt, applying crystal rotation of 15rpm through a crystal growth controller, cooling at the speed of 0.2 ℃/h, and obtaining BaBOF with the size of 14mm × 12mm, × 11mm after the crystal growth stops3A nonlinear optical crystal.
Example 29
BaBOF growth by vacuum packaging method3Nonlinear optical crystal:
BaBOF, a compound obtained according to example 113Filling the polycrystalline powder into a quartz tube with the diameter of 40mm, vacuumizing the quartz tube until the vacuum degree reaches 1 × 10-3Pa, sealing at high temperature, placing in a muffle furnace, heating to 650 ℃, keeping the temperature for 5 hours, then cooling to 350 ℃ at the speed of 0.1 ℃/h, and then rapidly cooling to room temperature at the speed of 8 ℃/h to obtain BaBOF with the size of 4mm × 3mm, × 2mm3A nonlinear optical crystal.
Example 30
BaBOF growth by vacuum packaging method3Nonlinear optical crystal:
BaBOF, a compound obtained according to example 13Polycrystalline powder and cosolvent H3BO3Mixing uniformly according to a molar ratio of 1:6, placing into a quartz tube with a diameter of 40mm, vacuumizing the quartz tube until the vacuum degree reaches 1 × 10-3Pa, sealing at high temperature, placing in a muffle furnace, heating to 550 ℃, keeping the temperature for 50 hours, then cooling to 350 ℃ at the speed of 2 ℃/h, and then rapidly cooling to room temperature at the speed of 10 ℃/h to obtain BaBOF with the size of 4mm × 2mm, × 2mm3A nonlinear optical crystal.
Example 31
BaBOF growth by vacuum packaging method3Nonlinear optical crystal:
BaBOF, a compound obtained according to example 13Polycrystalline powder and cosolvent B2O3Mixing uniformly according to a molar ratio of 1:1, placing into a quartz tube with a diameter of 40mm, vacuumizing the quartz tube until the vacuum degree reaches 1 × 10-3Pa, sealing at high temperature, placing in a muffle furnace, heating to 705 ℃, keeping the temperature for 120 hours, then cooling to 350 ℃ at the speed of 1 ℃/h, and then rapidly cooling to room temperature at the speed of 8 ℃/h to obtain BaBOF with the size of 5mm × 3mm, × 3mm3A nonlinear optical crystal.
Example 32
BaBOF growth by vacuum packaging method3Nonlinear optical crystal:
BaBO compound prepared according to example 1F3Uniformly mixing the polycrystalline powder and a cosolvent PbO according to the mol ratio of 1:2, filling the mixture into a quartz tube with the diameter of 40mm, vacuumizing the quartz tube until the vacuum degree reaches 1 × 10-3Pa, sealing at high temperature, placing in a muffle furnace, heating to 600 ℃, keeping the temperature for 48 hours, then cooling to 350 ℃ at the rate of 1.5 ℃/h, and then rapidly cooling to room temperature at the rate of 5 ℃/h to obtain BaBOF with the size of 4mm × 3mm, × 3mm3A nonlinear optical crystal.
Example 33
BaBOF growth by vacuum packaging method3Nonlinear optical crystal:
BaBOF, a compound obtained according to example 13Polycrystalline powder and cosolvent PbF2Mixing uniformly according to a molar ratio of 1:4, placing into a quartz tube with a diameter of 40mm, vacuumizing the quartz tube until the vacuum degree reaches 1 × 10-3Pa, sealing at high temperature, placing in a muffle furnace, heating to 580 deg.C, holding for 96 hr, cooling to 350 deg.C at a rate of 0.2 deg.C/h, and rapidly cooling to room temperature at a rate of 5 deg.C/h to obtain BaBOF with size of 5mm × 4mm × 3mm3A nonlinear optical crystal.
Example 34
Growing barium fluoborate nonlinear optical crystal by a hydrothermal method:
BaBOF, a compound prepared according to example 43Dissolving the polycrystalline powder in deionized water, and performing ultrasonic treatment on the incompletely dissolved mixture at the temperature of 60 ℃ to fully mix and dissolve the mixture; with HF and Ba (OH)2Adjusting the pH value to 8;
transferring the obtained mixed solution into a clean and pollution-free lining of a high-pressure reaction kettle with the volume of 100mL, and screwing and sealing the reaction kettle;
placing the high-pressure reaction kettle in a constant temperature box, heating to 150 ℃, keeping the temperature for 8 days, and then cooling to room temperature at a cooling rate of 5 ℃/day to obtain BaBOF with the size of 3mm × 3mm, × 2mm3A nonlinear optical crystal.
Example 35
Growing barium fluoborate nonlinear optical crystal by a hydrothermal method:
preparation according to example 8The resulting compound BaBOF3Dissolving the polycrystalline powder in deionized water, and performing ultrasonic treatment on the incompletely dissolved mixture at the temperature of 60 ℃ to fully mix and dissolve the mixture; with HF and Ba (OH)2Adjusting the pH value to 11;
transferring the obtained mixed solution into a clean and pollution-free lining of a high-pressure reaction kettle with the volume of 100mL, and screwing and sealing the reaction kettle;
placing the high-pressure reaction kettle in a constant temperature box, heating to 350 ℃, keeping the temperature for 5 days, and then cooling to room temperature at a cooling rate of 20 ℃/day to obtain BaBOF with the size of 4mm × 3mm, × 3mm3A nonlinear optical crystal.
Example 36
Room temperature solution method for growing barium fluoborate nonlinear optical crystal
The compound BaBOF prepared according to the step 93Placing the polycrystalline powder into a clean glass container, adding 20mL of deionized water, performing ultrasonic treatment to mix and dissolve the polycrystalline powder thoroughly, and using HF and Ba (OH)2Adjusting the pH value of the solution to 8, and filtering with filter paper to obtain a mixed solution;
placing the obtained mixed solution into a clean triangular flask, sealing the triangular flask with weighing paper, placing the triangular flask in a static environment without shaking, pollution and air convection, pricking a plurality of small holes on the sealing to adjust the evaporation rate of water in the aqueous solution, and standing the sealed mixed solution at room temperature for 5 days;
growing crystal particles on the bottom of the container until the size of the crystal particles is not obviously changed any more, and obtaining seed crystals;
selecting seed crystal with good quality, suspending in the prepared mixed solution, standing at room temperature for 30 days to obtain BaBOF with size of 11mm × 7mm × 7mm3A nonlinear optical crystal.
Example 37
Room temperature solution method for growing barium fluoborate nonlinear optical crystal
The compound BaBOF prepared according to the step 103Placing the polycrystalline powder into a clean glass container, adding 100mL of deionized water, performing ultrasonic treatment to mix and dissolve the polycrystalline powder thoroughly, and using HF and Ba (OH)2Adjusting the pH value of the solution to 11, and filtering the solution by using filter paper to obtain a solution;
b. placing the obtained solution in a clean triangular flask, sealing the triangular flask with weighing paper, placing the triangular flask in a static environment without shaking, pollution and air convection, pricking a plurality of small holes on the sealing to adjust the evaporation rate of water in the aqueous solution, and standing the sealed solution at room temperature for 5 days;
growing crystal particles on the bottom of the container until the size of the crystal particles is not obviously changed any more, and obtaining seed crystals;
selecting seed crystal with good quality, suspending in the prepared mixed solution, standing at room temperature for 10 days to obtain BaBOF with size of 4mm × 3mm × 3mm3A nonlinear optical crystal.
Example 38
Any BaBOF obtained in examples 19 to 373The crystal is processed in the matching direction, and is arranged at the position 3 as shown in figure 3, at room temperature, a Q-Nd YAG laser is used as a light source, the incident wavelength is 1064nm, and an infrared beam 2 with the wavelength of 1064nm is emitted by the Q-Nd YAG laser 1 and is emitted into BaBOF3And (3) single crystal 3, which generates green frequency doubling light with the wavelength of 532nm and has the output intensity of about 0.3 time of KDP under the same condition.
Example 39
Any BaBOF obtained in examples 19 to 373The crystal is processed in the matching direction, and is arranged at the position 3 as shown in figure 3, at room temperature, a Q-Nd YAG laser is used as a light source, the incident wavelength is 532nm, an infrared beam 2 with the wavelength of 532nm is emitted by the Q-adjusted Nd YAG laser 1 and is emitted into BaBOF3Single crystal 3, which produces light of 266nm wavelength doubled, has an output intensity of about 0.2 times that of BBO under the same conditions.

Claims (7)

1. A compound barium fluoborate is characterized in that the chemical formula of the compound is BaBOF3Molecular weight is 221.15, and the preparation method is solid phase synthesis method or vacuum packaging method.
2. The method for preparing the compound barium fluoborate according to claim 1, which is characterized by comprising the following steps:
the solid phase synthesis method is used for preparing a compound barium fluoborate:
uniformly mixing a Ba-containing compound, a B-containing compound and a F-containing compound according to the molar ratio of Ba to B to F of 1 to 3, putting the mixture into a platinum crucible, placing the platinum crucible into a muffle furnace, heating the mixture to 650 ℃ at 300 ℃ and keeping the temperature for 24 to 120 hours to obtain a BaBOF compound3The Ba-containing compound is BaF2、Ba(OH)2、BaCO3、Ba(NO3)2、Ba(HCO3)2Or Ba (BF)4)2(ii) a The compound containing B is H3BO3、B2O3、Ba(BF4)2(ii) a Containing F as compound BaF2Or Ba (BF)4)2；
The vacuum packaging method is used for preparing a compound barium fluoborate:
uniformly mixing Ba-containing compound, B-containing compound and F-containing compound according to molar ratio of Ba: B: F ═ 1:1:3, placing into a quartz tube, vacuumizing the quartz tube until the vacuum degree reaches 1 × 10−3Pa, sealing at high temperature, placing in a muffle furnace, heating to 650 ℃ at the rate of 5-10 ℃/h, and keeping the temperature for 24-120 hours to obtain a compound BaBOF3The Ba-containing compound is BaF2、Ba(OH)2、BaCO3、Ba(NO3)2、Ba(HCO3)2Or Ba (BF)4)2(ii) a The compound containing B is H3BO3、B2O3、Ba(BF4)2(ii) a Containing F as compound BaF2Or Ba (BF)4)2。
3. A barium fluoborate nonlinear optical crystal is characterized in that the chemical formula of the crystal is BaBOF3Molecular weight of 221.15, belonging to monoclinic system, space group ofP21Cell parameter ofa= 4.6145(17) Å，b= 4.3671(16) Å，c= 7.905(3) Å，β=105.519(6) ° unit cell volume 153.49(10) Å3。
4. The method for preparing a barium fluoroborate nonlinear optical crystal according to claim 3, wherein the crystal is grown by a melt method, a high-temperature melt method, a vacuum encapsulation method, a hydrothermal method or a room-temperature solution method;
the specific operation of growing the barium fluoborate nonlinear optical crystal by the melt method is carried out according to the following steps:
a. uniformly mixing a Ba-containing compound, a B-containing compound and a F-containing compound according to the molar ratio of Ba to B to F of 1 to 3, putting the mixture into a platinum crucible, placing the platinum crucible into a muffle furnace, heating the mixture to 650 ℃ at 500 ℃ and keeping the temperature for 24 to 120 hours to obtain a BaBOF compound3A polycrystalline powder, the Ba-containing compound being BaF2、Ba(OH)2、BaCO3、Ba(NO3)2、Ba(HCO3)2Or Ba (BF)4)2(ii) a The compound containing B is H3BO3、B2O3、Ba(BF4)2(ii) a Containing F as compound BaF2Or Ba (BF)4)2；
b. B, mixing the compound BaBOF prepared in the step a3Putting the polycrystalline powder into a platinum crucible, placing the platinum crucible in a muffle furnace, heating to 550-750 ℃, and keeping the temperature for 10-120 hours to obtain a mixed melt;
c. c, slowly reducing the temperature of the mixed melt obtained in the step b to 350 ℃ at the speed of 0.1-2 ℃/h, and rapidly reducing the temperature to room temperature at the speed of 5-10 ℃/h to obtain BaBOF3Seed crystal;
d. adopting a pulling method to grow crystals in a compound melt: c, fixing the seed crystal obtained in the step c on a seed crystal rod, lowering the seed crystal from the upper part of the mixed melt prepared in the step b, applying crystal rotation of 2-20rpm through a crystal growth controller, pulling the seed crystal at the speed of 1-10 mm/day, simultaneously cooling at the speed of 0.1-10 ℃/h, and after the crystal growth stops, obtaining BaBOF3A nonlinear optical crystal;
or growing crystals in a melt of the compound by kyropoulos: c, fixing the seed crystal obtained in the step c on a seed crystal rod, lowering the seed crystal from the upper part of the melt prepared in the step b, cooling at the speed of 0.1-10 ℃/h to ensure that the crystal grows for 5-15 hours, slowly lifting the crystal without deviating from the liquid level and continuing to growGrowing, repeating the steps, and obtaining BaBOF after crystal growth is stopped3A nonlinear optical crystal;
or growing crystals in a compound melt by the Bridgman method: c, placing the seed crystal prepared in the step c at the bottom of the crucible, and then placing the compound BaBOF prepared in the step a3Putting the polycrystal into a crucible, sealing the platinum crucible, raising the temperature of a growth furnace to 550-750 ℃, keeping the temperature for 10-120 hours, adjusting the position of the crucible to slightly melt the seed crystal, then reducing the crucible at the speed of 1-10 mm/day, simultaneously keeping the growth temperature unchanged, or reducing the temperature to 350 ℃ at the fastest speed of 3 ℃/h, and after the growth is finished, rapidly reducing the temperature to the room temperature at the speed of 5-10 ℃/h to obtain the BaBOF3A nonlinear optical crystal;
the specific operation of growing the barium fluoborate nonlinear optical crystal by the high-temperature melt method is carried out according to the following steps:
a. uniformly mixing a Ba-containing compound, a B-containing compound and a F-containing compound according to the molar ratio of Ba to B to F of 1 to 3, putting the mixture into a platinum crucible, placing the platinum crucible into a muffle furnace, heating the mixture to 650 ℃ at 500 ℃ and keeping the temperature for 24 to 120 hours to obtain a BaBOF compound3A polycrystalline powder, the Ba-containing compound being BaF2、Ba(OH)2、BaCO3、Ba(NO3)2、Ba(HCO3)2Or Ba (BF)4)2(ii) a The compound containing B is H3BO3、B2O3、Ba(BF4)2(ii) a The F-containing compound is BaF2Or Ba (BF)4)2；
b. B, mixing the compound BaBOF obtained in the step a3Uniformly mixing the polycrystalline powder and the fluxing agent according to the molar ratio of 1:0.1-6, then placing the mixture into a platinum crucible, heating to 550-; the cosolvent is H3BO3、B2O3PbO or PbF2；
c. Preparing seed crystals: b, placing the mixed melt obtained in the step b into a single crystal furnace, slowly cooling to 350 ℃ at the speed of 0.1-2 ℃/h, and then rapidly cooling to room temperature at the speed of 5-10 ℃/h to obtain BaBOF3Seed crystal;
d. growing a crystal: c, fixing the seed crystal obtained in the step c on a seed crystal rod, feeding the seed crystal from the upper part of the mixed melt prepared in the step b, applying crystal rotation of 2-20rpm through a crystal growth controller, cooling at the speed of 0.1-3 ℃/h, and obtaining BaBOF after crystal growth is stopped3A nonlinear optical crystal;
the specific operation of growing the barium fluoborate nonlinear optical crystal by the vacuum packaging method is carried out according to the following steps:
a. uniformly mixing a Ba-containing compound, a B-containing compound and a F-containing compound according to the molar ratio of Ba to B to F of 1 to 3, putting the mixture into a platinum crucible, placing the platinum crucible into a muffle furnace, heating the mixture to 650 ℃ at 500 ℃ and keeping the temperature for 24 to 120 hours to obtain a BaBOF compound3A polycrystalline powder, the Ba-containing compound being BaF2、Ba(OH)2、BaCO3、Ba(NO3)2、Ba(HCO3)2Or Ba (BF)4)2(ii) a The compound containing B is H3BO3、B2O3、Ba(BF4)2(ii) a The F-containing compound is BaF2Or Ba (BF)4)2；
b. B, mixing the compound BaBOF obtained in the step a3Uniformly mixing the polycrystalline powder and the fluxing agent according to the molar ratio of 0-1:0.1-6, placing the mixture into a quartz tube, placing the quartz tube into a muffle furnace after high-temperature sealing, heating to 550-3The cosolvent is H3BO3、B2O3PbO or PbF2；
The specific operation of the hydrothermal method for growing the barium fluoborate nonlinear optical crystal is carried out according to the following steps:
a. uniformly mixing a Ba-containing compound, a B-containing compound and a F-containing compound according to the molar ratio of Ba to B to F of 1 to 3, putting the mixture into a platinum crucible, placing the platinum crucible into a muffle furnace, heating the mixture to 650 ℃ at 500 ℃ and keeping the temperature for 24 to 120 hours to obtain a BaBOF compound3A polycrystalline powder, the Ba-containing compound being BaF2、Ba(OH)2、BaCO3、Ba(NO3)2、Ba(HCO3)2Or Ba (BF)4)2(ii) a The compound containing B is H3BO3、B2O3、Ba(BF4)2(ii) a The F-containing compound is BaF2Or Ba (BF)4)2；
b. B, mixing the compound BaBOF obtained in the step a3Dissolving the polycrystalline powder in deionized water, subjecting the incompletely dissolved mixture to ultrasonic treatment at 60 deg.C to thoroughly mix and dissolve, and dissolving with HF and Ba (OH)2Adjusting the pH value to 8-11;
c. b, transferring the mixed solution obtained in the step b into a clean and pollution-free lining of a high-pressure reaction kettle with the volume of 100mL, and screwing and sealing the reaction kettle;
d. placing the high-pressure reaction kettle in a constant temperature box, heating to 150-350 ℃, keeping the temperature for 5-8 days, and then cooling to room temperature at the cooling rate of 5-20 ℃/day to obtain BaBOF3A nonlinear optical crystal;
the room temperature solution method for growing the barium fluoborate nonlinear optical crystal comprises the following specific operations:
a. uniformly mixing a Ba-containing compound, a B-containing compound and a F-containing compound according to the molar ratio of Ba to B to F of 1 to 3, putting the mixture into a platinum crucible, placing the platinum crucible into a muffle furnace, heating the mixture to 650 ℃ at 500 ℃ and keeping the temperature for 24 to 120 hours to obtain a BaBOF compound3A polycrystalline powder, the Ba-containing compound being BaF2、Ba(OH)2、BaCO3、Ba(NO3)2、Ba(HCO3)2Or Ba (BF)4)2(ii) a The compound containing B is H3BO3、B2O3、Ba(BF4)2(ii) a The F-containing compound is BaF2Or Ba (BF)4)2；
b. B, mixing the compound BaBOF obtained in the step a3Placing the polycrystalline powder into a clean glass container, adding 20-100mL deionized water, performing ultrasonic treatment to mix thoroughly and dissolve, and dissolving with HF and Ba (OH)2Adjusting pH to 8-11, and filtering with filter paper to obtain mixed solution;
c. b, placing the mixed solution obtained in the step b into a clean glass container, sealing the container by using weighing paper, placing the container in a static environment without shaking, pollution and air convection, pricking a plurality of small holes on the seal to adjust the evaporation rate of water in the water solution, and standing the container for 5 to 20 days at room temperature;
d. c, growing crystal particles on the bottom of the container by the solution in the step c until the size of the crystal particles is not obviously changed, and obtaining seed crystals;
e. selecting seed crystals with better quality in the step d, suspending the seed crystals in the mixed solution prepared in the step b, standing and growing for 10-30 days at room temperature to obtain BaBOF3A nonlinear optical crystal.
5. Use of the barium fluoroborate nonlinear optical crystal of claim 3 in preparation of harmonic light output by frequency 2, 3, 4, and 5 doubling of 1064nm fundamental frequency light output by a Nd: YAG laser.
6. Use of the barium fluoroborate nonlinear optical crystal of claim 5 in the preparation of a crystal that produces deep ultraviolet multiplied light output below 200 nm.
7. Use of the compound barium fluoroborate nonlinear optical crystal of claim 3 in the preparation of a frequency doubler generator, an upper or lower frequency converter, or an optical parametric oscillator.
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