CN112111787A - Compound magnesium pentafluoride, magnesium pentafluoride nonlinear optical crystal, preparation method and application - Google Patents

Compound magnesium pentafluoride, magnesium pentafluoride nonlinear optical crystal, preparation method and application Download PDF

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CN112111787A
CN112111787A CN202011061616.1A CN202011061616A CN112111787A CN 112111787 A CN112111787 A CN 112111787A CN 202011061616 A CN202011061616 A CN 202011061616A CN 112111787 A CN112111787 A CN 112111787A
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mgb
compound
quartz tube
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潘世烈
米日丁·穆太力普
夏明�
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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
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    • 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
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    • C30B7/00—Single-crystal growth from solutions using solvents which are liquid at normal temperature, e.g. aqueous solutions
    • C30B7/10—Single-crystal growth from solutions using solvents which are liquid at normal temperature, e.g. aqueous solutions by application of pressure, e.g. hydrothermal processes
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    • 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
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Abstract

The invention relates to a compound magnesium pentafluoride, a magnesium pentafluoride nonlinear optical crystal, a preparation method and application thereof, wherein the chemical formula of the compound is MgB5O7F3Molecular weight is 247.351, and the preparation method adopts a solid phase reaction method; the chemical formula of the crystal is MgB5O7F3Molecular weight of 247.351, crystal belonging to orthorhombic system, space groupCmc21The unit cell parameters are a =9.87679(15) A, b =8.37048(9) A, c =7.94544(12) A,Z=4，V=656.877(3)Å3. MgB with the size of centimeter grade is obtained by the method5O7F3The nonlinear optical crystal is used for preparing harmonic light output of 1064nm fundamental frequency light output by a Nd-YAG laser by 2 frequency doubling or 3 frequency doubling or 4 frequency doubling or 5 frequency doubling or 6 frequency doubling or generating deep ultraviolet frequency doubling light output lower than 200nm or is used for preparing a frequency doubling generator, an upper or lower frequency converter or an optical parametric oscillator. The MgB5O7F3The nonlinear optical crystal has the advantages of wider light-transmitting wave band, stable physical and chemical properties, high mechanical hardness, difficult fragmentation and deliquescence, easy cutting, polishing processing and storage and the like.

Description

Compound magnesium pentafluoride, magnesium pentafluoride nonlinear optical crystal, preparation method and application
Technical Field
The invention relates to a compound magnesium pentafluoride trifluoride pentaborate, a magnesium pentafluoride nonlinear optical crystal, a preparation method and application thereof.
Background
The development of all-solid-state deep ultraviolet laser light sources along with the strong demand of 193nm lithography, micro-nano fine laser processing, ultra-high energy resolution photoelectron spectrometers, photoelectron emission microscopes and other modern instruments on deep ultraviolet laser sources (generally, the wavelength is shorter than 200nm) has become a hot spot of recent research in the international laser science community. The development of all-solid-state deep ultraviolet laser light sources, and the deep ultraviolet nonlinear optical crystal is a very critical element.
The ultraviolet and deep ultraviolet nonlinear optical crystal applied in the industry at present mainly comprises LiB3O5(LBO)、CsB3O5(CBO)、CsLiB6O10(CLBO)、BaB2O4(BBO) and KBe2BO3F2(KBBF) crystal. The LBO crystal has wide light transmission range, high optical uniformity, large effective frequency doubling coefficient (3KDP) and high damage threshold (18.9 GW/cm)2). But it cannot achieve phase matching in the deep ultraviolet region due to its relatively small birefringence (Δ n ═ 0.04-0.05), and the shortest doubling wavelength is 276 nm. Like LBO crystals, CBO and CLBO crystals are limited in application in the deep ultraviolet region due to their relatively small birefringence. Although the BBO crystal has larger frequency multiplication coefficient and birefringence, the BBO crystal has the shortest frequency multiplication wavelength of 204.8nm due to the relatively higher ultraviolet absorption cut-off edge (189nm), thereby limiting the application of the BBO crystal in the deep ultraviolet region. KBBF can realize direct six-frequency-multiplication output of 1064nm fundamental frequency light, but because KBBF has a layered growth habit, large-size crystal growth difficulty is high, and the application of KBBF is limited to a certain extent.Therefore, the development of a novel deep ultraviolet nonlinear optical crystal with excellent comprehensive performance is urgently needed.
Disclosure of Invention
The invention aims to provide a compound magnesium pentafluoride, which has a chemical formula of MgB5O7F3And the molecular weight is 247.351. The preparation method adopts a solid-phase reaction method.
Another object of the present invention is to provide magnesium pentafluoride MgB5O7F3A nonlinear optical crystal of the formula MgB5O7F3Molecular weight of 247.351, crystal belonging to orthorhombic system, space group Cmc21Cell parameter of
Figure BDA0002712551180000011
Figure BDA0002712551180000012
The invention also aims to provide a preparation method of the magnesium pentafluoride borate nonlinear optical crystal, which adopts a fluxing agent method, a Bridgman-Stockbarge method, a room-temperature solution method and a solvothermal method to grow the crystal.
It is a further object of the present invention to provide magnesium pentafluoride MgB5O7F3Use of a nonlinear optical crystal.
The invention relates to a compound magnesium pentafluoride trifluoride, which has a chemical formula of MgB5O7F3Molecular weight is 247.351, and the preparation method adopts solid phase reaction method.
The preparation method of the compound magnesium pentafluoride borate comprises the following steps:
the Mg-containing compound is Mg (BF)4)2The compound containing B is H3BO3And B2O3The F-containing compound is Mg (BF)4)2Uniformly mixing the components according to the mol ratio of Mg to B to F of 0.5-2 to 5-7 to 2-4, sealing the mixture in a hydrothermal kettle or a quartz tube, putting the mixture in a resistance furnace, heating the mixture to 200 ℃ and 650 ℃ at the speed of 10-30 ℃/h, keeping the temperature for 10-48 hours, and then heating the mixture at 1 ℃ for 1 hourReducing the speed of minus 10 ℃/h to 25 ℃, and opening a hydrothermal kettle or a quartz tube to obtain a compound MgB5O7F3。
A magnesium pentafluoride non-linear optical crystal has a chemical formula of MgB5O7F3Molecular weight of 247.351, crystal belonging to orthorhombic system, space group Cmc21Cell parameter of
Figure BDA0002712551180000021
Figure BDA0002712551180000022
The preparation method of the magnesium pentafluoride non-linear optical crystal adopts a fluxing agent method, a Bridgman-Stockbarge method, a room-temperature solution method or a solvothermal method to grow the crystal:
the cosolvent method is used for growing magnesium pentafluoride non-linear optical crystal crystals, and the specific operation is carried out according to the following steps:
a. the Mg-containing compound is Mg (BF)4)2The compound containing B is H3BO3And B2O3The F-containing compound is Mg (BF)4)2Uniformly mixing Mg, B and F according to the mol ratio of 0.5-2: 5-7: 2-4, sealing in a hydrothermal kettle or a quartz tube, placing in a resistance furnace, heating to 200 ℃ and 650 ℃ at the speed of 10-30 ℃/h, keeping the temperature for 10-48 hours, then cooling to 25 ℃ at the speed of 1-10 ℃/h, and opening the hydrothermal kettle or the quartz tube to obtain a compound MgB5O7F3；
b. B, mixing the compound MgB obtained in the step a5O7F3Putting into a quartz tube with diameter of 10mm, vacuumizing the quartz tube until the vacuum degree reaches 1 × 10-3Pa, vacuum packaging with a flame gun, placing into a muffle furnace, heating to 200 ℃ and 650 ℃ at a speed of 10-30 ℃/h, keeping the temperature for 12-60 hours, then cooling to 25 ℃ at a speed of 1-5 ℃/h, opening a quartz tube to obtain MgB5O7F3Seed crystals of the crystals;
c. the MgB obtained in the step b5O7F3The seed crystal is placed in a containerThe bottom of the quartz tube is filled with the compound MgB obtained in step a5O7F3The fluxing agent is NaF or NaBF4、NaF-H3BO3、NaF-B2O3、H3BO3Or B2O3Mixing at a molar ratio of 1: 1-5, placing into a quartz tube, vacuumizing the quartz tube to a vacuum degree of 1 × 10-3Pa, vacuum packaging by using a flame gun;
d. sealing the container in the step c or adding 10-100mL of solvent as deionized water, resealing with anhydrous ethanol or hydrofluoric acid, placing into a resistance furnace, heating to 200-650 ℃ at a rate of 20-40 ℃/h, keeping the temperature for 12-60 hours, cooling to 50 ℃ at a rate of 1-3 ℃/day, cooling to 25 ℃ at a rate of 1-10 ℃/h, and opening the container to obtain MgB with the size of 1-20mm5O7F3A nonlinear optical crystal;
the magnesium pentafluoride non-linear optical crystal is grown by the Bridgman-Stockbarge method, and the specific operation is carried out according to the following steps:
a. the Mg-containing compound is Mg (BF)4)2The compound containing B is H3BO3And B2O3The F-containing compound is Mg (BF)4)2Uniformly mixing Mg, B and F according to the mol ratio of 0.5-2: 5-7: 2-4, sealing in a hydrothermal kettle or a quartz tube, placing in a resistance furnace, heating to 200 ℃ and 650 ℃ at the speed of 10-30 ℃/h, keeping the temperature for 10-48 hours, then cooling to 25 ℃ at the speed of 1-10 ℃/h, and opening the hydrothermal kettle or the quartz tube to obtain a compound MgB5O7F3；
b. The compound MgB obtained is5O7F3Sealing in a hydrothermal kettle, placing in a drying oven, heating to 200 deg.C at a rate of 20 deg.C/h, holding for 10 hr, cooling to 25 deg.C at a rate of 1 deg.C/h, and opening the hydrothermal kettle to obtain MgB5O7F3Seed crystals of the crystals;
c. placing the obtained seed crystal at the bottom of an iridium crucible, and then putting the obtained compound MgB5O7F3Putting the crucible into an iridium crucible;
d. sealing an iridium crucibleSealing and placing in a crucible descending furnace, heating to 600 ℃ of 300-5O7F3A nonlinear optical crystal;
the room temperature solution method for growing magnesium pentafluoride non-linear optical crystal crystals comprises the following steps:
a. the Mg-containing compound is Mg (BF)4)2The compound containing B is H3BO3And B2O3The F-containing compound is Mg (BF)4)2Uniformly mixing Mg, B and F according to the mol ratio of 0.5-2: 5-7: 2-4, sealing in a hydrothermal kettle or a quartz tube, placing in a resistance furnace, heating to 200 ℃ and 650 ℃ at the speed of 10-30 ℃/h, keeping the temperature for 10-48 hours, then cooling to 25 ℃ at the speed of 1-10 ℃/h, and opening the hydrothermal kettle or the quartz tube to obtain a compound MgB5O7F3；
b. B, mixing the compound MgB obtained in the step a5O7F3Sealing in a hydrothermal kettle, placing in a drying box, heating to 200 ℃./h at a rate of 10-30 ℃/h, keeping the temperature for 10-48 hours, then cooling to 25 ℃ at a rate of 1-5 ℃/h, opening the hydrothermal kettle or a quartz tube to obtain MgB5O7F3Seed crystals of the crystals;
c. b, putting the seed crystal obtained in the step b at the bottom of a clean container, and then putting the obtained compound MgB5O7F3Putting into a container;
d. adding 10-100mL solvent deionized water, absolute ethyl alcohol or hydrofluoric acid into the container in the step c, then carrying out ultrasonic treatment to fully mix and dissolve the solvent, adjusting the pH value of the solution to 1-11, filtering the solution by qualitative filter paper, sealing the opening by a polyvinyl chloride film, placing the opening in a static environment without shaking, pollution and air convection, pricking a plurality of small holes to adjust the volatilization rate of the solvent in the solution,standing at room temperature until growth is finished to obtain MgB with size of 1-20mm5O7F3A nonlinear optical crystal;
the solvent thermal method is used for growing magnesium pentafluoride non-linear optical crystal crystals, and the specific operation is carried out according to the following steps:
a. the Mg-containing compound is Mg (BF)4)2The compound containing B is H3BO3And B2O3The F-containing compound is Mg (BF)4)2Uniformly mixing Mg, B and F according to the mol ratio of 0.5-2: 5-7: 2-4, sealing in a hydrothermal kettle or a quartz tube, placing in a resistance furnace, heating to 200 ℃ and 650 ℃ at the speed of 10-30 ℃/h, keeping the temperature for 10-48 hours, then cooling to 25 ℃ at the speed of 1-10 ℃/h, and opening the hydrothermal kettle or the quartz tube to obtain a compound MgB5O7F3；
b. B, mixing the compound MgB obtained in the step a5O7F3Sealing in a hydrothermal kettle, heating to 200 ℃./h at 10-30 ℃/h in a drying box, keeping the temperature for 10-48 h, cooling to 25 ℃ at 1-5 ℃/h, and opening the hydrothermal kettle or a quartz tube to obtain MgB5O7F3Seed crystals of the crystals;
c. b, putting the seed crystal obtained in the step b at the bottom of a polytetrafluoroethylene lining of a clean and pollution-free hydrothermal kettle with the volume of 23mL, and then putting the obtained compound MgB5O7F3Putting the mixture into a polytetrafluoroethylene lining;
d. adding deionized water as a solvent into the polytetrafluoroethylene lining, and screwing and sealing the hydrothermal kettle; placing the hydrothermal kettle in a drying oven, heating to 150 ℃ at the speed of 20 ℃/h, keeping the temperature for 24 hours, and then cooling to 130 ℃ at the speed of 2 ℃/day; then reducing the temperature to 25 ℃ at the speed of 2 ℃/h, and opening the hydrothermal kettle to obtain MgB5O7F3A nonlinear optical crystal.
Fluxing agent NaF-H in step c of the cosolvent method3BO3NaF and H in the system3BO3The molar ratio of (A) to (B) is 1-3: 1-5; NaF-B2O3NaF and B in the system2O3The molar ratio of (A) to (B) is 1-2: 1-4.
The magnesium pentafluoride borate nonlinear optical crystal is used for outputting 2-frequency or 3-frequency or 4-frequency or 5-frequency or 6-frequency doubled harmonic light by preparing 1064nm fundamental frequency light output by a Nd: YAG laser.
The application of the magnesium pentafluoride borate nonlinear optical crystal in preparing the optical crystal which generates deep ultraviolet frequency doubling light output below 200 nm.
The magnesium pentafluoride borate nonlinear optical crystal is used for preparing a frequency doubling generator, an upper or lower frequency converter or an optical parametric oscillator.
The compound magnesium pentafluoride and magnesium pentafluoride nonlinear optical crystal and the preparation method and the application thereof are disclosed, wherein in the method, a container is a platinum crucible, an iridium crucible, a ceramic crucible, a quartz tube, a conical flask and a beaker, and the lining is a polytetrafluoroethylene lining or a hydrothermal kettle with a stainless steel lining provided with a platinum sleeve. When the container is a quartz tube, the container needs to be vacuumized before sealing, so that the quartz tube is prevented from being cracked due to gas released 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.
The resistance furnace is a muffle furnace or a drying box.
By adopting the preparation method of the magnesium pentafluoride non-linear optical crystal, MgB with the size of centimeter grade is obtained by the method5O7F3The nonlinear optical crystal has no obvious layered growth habit, and by using large-size crucible or container and prolonging the growth period of the crystal, the nonlinear optical crystal MgB with corresponding large size can be obtained5O7F3In the MgB5O7F3The 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 MgB obtained by the preparation method of the magnesium pentafluoride borate nonlinear optical crystal5O7F3Nonlinear optical crystal, rootAccording to the crystallography data of crystal, the crystal blank is oriented, the crystal is cut according to required angle, thickness and section size, the light-passing surface of the crystal is polished, and the MgB can be used as a nonlinear optical device5O7F3The nonlinear optical crystal has the advantages of wider light-transmitting wave band, stable physical and chemical properties, high mechanical hardness, difficult fragmentation and deliquescence, easy cutting, polishing processing and storage and the like.
Drawings
FIG. 1 shows MgB, a compound of the present invention5O7F3The powder XRD spectrogram is consistent with the theoretical XRD spectrogram, and the compound MgB is proved5O7F3Presence of (a);
FIG. 2 is MgB of the present invention5O7F3A structure of a crystal;
FIG. 3 is MgB of the present invention5O7F3Working principle diagram of nonlinear optical device made of crystal, wherein 1 is laser, 2 is emitted light beam, and 3 is MgB5O7F3Crystal, 4 is emergent light beam, and 5 is filter.
Detailed Description
Example 1
Preparation of the compound:
according to the reaction formula: 3Mg (BF)4)2+7B2O3→3MgB5O7F3+5BF3↓preparationmethod and solid phase reaction method adopted for synthesizing compound MgB5O7F3：
Mixing Mg (BF)4)2，B2O3Mixing uniformly according to a molar ratio of 3:7, placing into a quartz tube with a diameter of 10mm, vacuumizing the quartz tube until the vacuum degree reaches 1 × 10-3Pa, vacuum packaging with a flame gun, placing into a muffle furnace, heating to 650 deg.C at 30 deg.C/h, holding for 12 hr, cooling to 25 deg.C at 6 deg.C/h, and opening a quartz tube to obtain MgB compound5O7F3。
Example 2
Preparation of the compound:
pressing reverselyThe formula should be: 3Mg (BF)4)2+14H3BO3→3MgB5O7F3+5BF3↑+21H2O ↓, and solid phase reaction process to synthesize MgB compound5O7F3：
Mixing Mg (BF)4)2，H3BO3Uniformly mixing the materials according to a molar ratio of 3:14, putting the mixture into a clean and pollution-free polytetrafluoroethylene lining of a hydrothermal kettle with a volume of 23mL, tightly screwing and sealing the hydrothermal kettle, placing the hydrothermal kettle in a drying box, heating the hydrothermal kettle to 200 ℃ at a speed of 35 ℃/h, keeping the temperature for 60 hours, then cooling the hydrothermal kettle to 25 ℃ at a speed of 6 ℃/h, and opening the hydrothermal kettle to obtain a compound MgB5O7F3。
Example 3
Room temperature solution process of synthesizing MgB5O7F3Nonlinear optical crystal:
according to the reaction formula: 3Mg (BF)4)2+7B2O3→3MgB5O7F3+5BF3↓ [ O ] synthetic MgB5O7F3Compounds, the specific procedure was carried out according to example 1;
the compound MgB obtained is5O7F3Sealing in a hydrothermal kettle, placing in a drying oven, heating to 200 deg.C at a rate of 20 deg.C/h, holding for 10 hr, cooling to 25 deg.C at a rate of 1 deg.C/h, and opening the hydrothermal kettle to obtain MgB5O7F3Seed crystals of the crystals;
placing the obtained seed crystal at the bottom of a clean beaker, and then putting the obtained compound MgB5O7F3Putting into a beaker;
adding 5mL of hydrofluoric acid serving as a solvent into a beaker, carrying out ultrasonic treatment to fully mix and dissolve the hydrofluoric acid, adjusting the pH value of the solution to 4-6, filtering the solution by using qualitative filter paper, sealing the solution by using a polyvinyl chloride film, putting the sealed solution in a static environment without shaking, pollution and air convection, pricking a plurality of small holes on the sealed solution to adjust the volatilization rate of the solvent in the solution, standing the sealed solution at room temperature, and obtaining MgB with the size of phi 3mm multiplied by 4mm multiplied by 5mm after the growth is finished5O7F3A nonlinear optical crystal.
Example 4
Room temperature solution process of synthesizing MgB5O7F3Nonlinear optical crystal:
according to the reaction formula: 3Mg (BF)4)2+14H3BO3→3MgB5O7F3+5BF3↑+21H2O ↓syntheticMgB5O7F3Compounds, the specific procedure was carried out according to example 1;
the compound MgB obtained is5O7F3Putting into a quartz tube with diameter of 10mm, vacuumizing the quartz tube until the vacuum degree reaches 1 × 10-3Pa, vacuum packaging with a flame gun, placing into a muffle furnace, heating to 650 deg.C at 40 deg.C/h, holding for 48 hr, cooling to 25 deg.C at 5 deg.C/h, and opening quartz tube to obtain MgB5O7F3Seed crystals of the crystals;
placing the obtained seed crystal at the bottom of the container, and then adding the obtained compound MgB5O7F3Putting into a conical flask;
adding 100mL of absolute ethyl alcohol into a conical flask, then carrying out ultrasonic treatment to fully mix and dissolve the absolute ethyl alcohol, filtering the mixture by using qualitative filter paper, sealing the mixture by using a polyvinyl chloride film, placing the mixture in a static environment without shaking, pollution or air convection, pricking a plurality of small holes on the seal to adjust the volatilization rate of a solvent in the solution, standing the mixture at room temperature, and obtaining MgB with the size of phi 5mm multiplied by 2mm multiplied by 3mm after the growth is finished5O7F3A nonlinear optical crystal.
Example 5
Room temperature solution process of synthesizing MgB5O7F3Nonlinear optical crystal:
according to the reaction formula: 3Mg (BF)4)2+14H3BO3→3MgB5O7F3+5BF3↑+21H2O ↓syntheticMgB5O7F3Compounds, the specific procedure was carried out according to example 2;
the compound MgB obtained is5O7F3Sealing in a hydrothermal kettle, placing in a drying oven, heating to 280 deg.C at a rate of 30 deg.C/h, holding the temperature for 20 hr, cooling to 25 deg.C at a rate of 2 deg.C/h, and opening the hydrothermal kettle to obtain MgB5O7F3Seed crystals of the crystals;
placing the obtained seed crystal at the bottom of a beaker, and then putting the compound MgB obtained in the step a5O7F3Putting into a beaker;
adding deionized water into a beaker, performing ultrasonic treatment to fully mix and dissolve the deionized water, filtering the mixture by qualitative filter paper, sealing the opening by a polyvinyl chloride film, putting the beaker in a static environment without shaking, pollution and air convection, pricking a plurality of small holes on the sealed opening to adjust the volatilization rate of a solvent in the solution, standing the beaker at room temperature, and obtaining MgB with the size of phi 6mm multiplied by 5mm after the growth is finished5O7F3A nonlinear optical crystal.
Example 6
Growing MgB by fluxing agent method5O7F3Crystal:
according to the reaction formula: 3Mg (BF)4)2+7B2O3→3MgB5O7F3+5BF3↓ [ O ] synthetic MgB5O7F3Compounds, the specific procedure was carried out according to example 2;
the compound MgB obtained is5O7F3Putting into a quartz tube with diameter of 10mm, vacuumizing the quartz tube until the vacuum degree reaches 1 × 10-3Pa, vacuum packaging with a flame gun, placing into a muffle furnace, heating to 400 deg.C at a rate of 30 deg.C/h, holding the temperature for 30 hr, cooling to 25 deg.C at a rate of 2 deg.C/h, and opening a quartz tube to obtain MgB5O7F3Seed crystals of the crystals;
the obtained MgB5O7F3Seed crystals are placed at the bottom of the container, and the resulting compound MgB is then added5O7F3Mixing with flux NaF at a molar ratio of 1: 5, placing into a quartz tube, vacuumizing the quartz tube to vacuum degreeTo 1X 10-3Pa, vacuum packaging by using a flame gun;
then putting the mixture into a muffle furnace, raising the temperature to 500 ℃ at the speed of 30 ℃/h, keeping the temperature for 36 hours, then lowering the temperature to 450 ℃ at the speed of 1.5 ℃/day, lowering the temperature to 25 ℃ at the speed of 2 ℃/h, and cutting a quartz tube to obtain MgB with the size of phi 5mm multiplied by 5mm5O7F3A nonlinear optical crystal.
Example 7
Growing MgB by fluxing agent method5O7F3Crystal:
according to the reaction formula: 3Mg (BF)4)2+7B2O3→3MgB5O7F3+5BF3↓ [ O ] synthetic MgB5O7F3Compounds, the specific procedure was carried out according to example 1;
the compound MgB obtained is5O7F3Putting into a quartz tube with diameter of 10mm, vacuumizing the quartz tube until the vacuum degree reaches 1 × 10-3Pa, vacuum packaging with a flame gun, placing into a muffle furnace, heating to 300 deg.C at a rate of 20 deg.C/h, holding for 10 hr, cooling to 25 deg.C at a rate of 1 deg.C/h, and opening a quartz tube to obtain MgB5O7F3Seed crystals of the crystals;
firstly MgB5O7F3The seed crystal of the crystal is placed at the bottom of a quartz tube with the diameter of phi 10mm, and then a compound MgB is put5O7F3With fluxing agent NaF: H3BO3Mixing according to a molar ratio of 1: 1, wherein a cosolvent NaF: H3BO3NaF and H in (1)3BO3Is 1: 1, putting the quartz tube into the quartz tube, vacuumizing the quartz tube until the vacuum degree reaches 1 multiplied by 10-3Pa, vacuum packaging by using a flame gun;
then putting the mixture into a muffle furnace, heating to 450 ℃ at the speed of 30 ℃/h, keeping the temperature for 24 hours, then cooling to 400 ℃ at the speed of 1.5 ℃/day, then cooling to 25 ℃ at the speed of 2 ℃/h, and cutting a quartz tube to obtain MgB with the size of phi 10mm multiplied by 7mm multiplied by 6mm5O7F3A nonlinear optical crystal.
Example 8
Growing MgB by fluxing agent method5O7F3Crystal:
according to the reaction formula: 3Mg (BF)4)2+14H3BO3→3MgB5O7F3+5BF3↑+21H2O ↓syntheticMgB5O7F3Compounds, the specific procedure was carried out according to example 2;
the compound MgB obtained is5O7F3Putting into a quartz tube with diameter of 10mm, vacuumizing the quartz tube until the vacuum degree reaches 1 × 10-3Pa, vacuum packaging with a flame gun, placing into a muffle furnace, heating to 500 deg.C at 40 deg.C/h, holding for 40 hr, cooling to 25 deg.C at 4 deg.C/h, and opening quartz tube to obtain MgB5O7F3Seed crystals of the crystals;
the obtained MgB5O7F3Seed crystals are placed at the bottom of the container, and the resulting compound MgB is then added5O7F3The fluxing agent is NaF: B2O3Mixing according to a molar ratio of 1: 3, wherein NaF-B2O3NaF and B in the system2O3Is 1: 2, putting the quartz tube into the quartz tube, vacuumizing the quartz tube until the vacuum degree reaches 1 multiplied by 10-3Pa, vacuum packaging by using a flame gun;
then putting the mixture into a muffle furnace, heating to 450 ℃ at the speed of 40 ℃/h, keeping the temperature for 20 hours, then cooling to 400 ℃ at the speed of 2 ℃/day, then cooling to 25 ℃ at the speed of 3 ℃/h, and cutting a quartz tube to obtain MgB with the size of phi 5mm multiplied by 6mm multiplied by 8mm5O7F3A nonlinear optical crystal.
Example 9
Growing MgB by fluxing agent method5O7F3Crystal:
according to the reaction formula: 3Mg (BF)4)2+14H3BO3→3MgB5O7F3+5BF3↑+21H2O ↓syntheticMgB5O7F3Compounds, detailed procedure in accordance with example 1Carrying out the following steps;
the compound MgB obtained is5O7F3Putting into a quartz tube with diameter of 10mm, vacuumizing the quartz tube until the vacuum degree reaches 1 × 10-3Pa, vacuum packaging with a flame gun, placing into a muffle furnace, placing into the muffle furnace, heating to 300 deg.C at a rate of 25 deg.C/h, holding the temperature for 30 hr, cooling to 25 deg.C at a rate of 3 deg.C/h, and opening a quartz tube to obtain MgB5O7F3Seed crystals of the crystals;
firstly MgB5O7F3The seed crystal of the crystal is placed at the bottom of a quartz tube with the diameter of 10mm, and then MgB is put in a molar ratio of 1: 55O7F3Compound and flux NaBF4Mixing, placing into a quartz tube, vacuumizing the quartz tube to a vacuum degree of 1 × 10- 3Pa, vacuum packaging by using a flame gun;
then putting the mixture into a muffle furnace, heating to 600 ℃ at the speed of 40 ℃/h, keeping the temperature for 48 hours, then cooling to 550 ℃ at the speed of 3 ℃/day, then cooling to 25 ℃ at the speed of 10 ℃/h, and cutting a quartz tube to obtain MgB with the size of phi 8mm multiplied by 7mm multiplied by 6mm5O7F3A nonlinear optical crystal.
Example 10
Growing MgB by fluxing agent method5O7F3Crystal:
according to the reaction formula: 3Mg (BF)4)2+7B2O3→3MgB5O7F3+5BF3↓ [ O ] synthetic MgB5O7F3Compounds, the specific procedure was carried out according to example 1;
the compound MgB obtained is5O7F3Sealing in a hydrothermal kettle, placing in a drying oven, heating to 210 deg.C at a rate of 25 deg.C/h, holding the temperature for 15 hr, cooling to 25 deg.C at a rate of 3 deg.C/h, and opening the hydrothermal kettle to obtain MgB5O7F3Seed crystals of the crystals;
firstly MgB5O7F3The seed crystal of the crystal is placed at the bottom of a quartz tube with the diameter of phi 10mm, and then a compound MgB is put5O7F3With fluxing agent NaF: H3BO3Mixing according to a molar ratio of 1: 5, wherein a cosolvent NaF: H3BO3NaF and H in (1)3BO3The molar ratio of the raw materials is 2: 3, the raw materials are put into a quartz tube, the quartz tube is vacuumized, and the vacuum degree reaches 1 multiplied by 10-3Pa, vacuum packaging by using a flame gun;
then putting the mixture into a muffle furnace, heating to 450 ℃ at the speed of 30 ℃/h, keeping the temperature for 24 hours, then cooling to 400 ℃ at the speed of 1.5 ℃/day, then cooling to 25 ℃ at the speed of 2 ℃/h, and cutting a quartz tube to obtain MgB with the size of phi 5mm multiplied by 4mm5O7F3A nonlinear optical crystal.
Example 11
Growing MgB by fluxing agent method5O7F3Crystal:
according to the reaction formula: 3Mg (BF)4)2+7B2O3→3MgB5O7F3+5BF3↓ [ O ] synthetic MgB5O7F3Compounds, the specific procedure was carried out according to example 2;
the compound MgB obtained is5O7F3Putting into a quartz tube with diameter of 10mm, vacuumizing the quartz tube until the vacuum degree reaches 1 × 10-3Pa, vacuum packaging with a flame gun, placing into a muffle furnace, heating to 500 deg.C at 40 deg.C/h, holding for 46 hr, cooling to 25 deg.C at 4 deg.C/h, and opening quartz tube to obtain MgB5O7F3Seed crystals of the crystals;
the obtained MgB5O7F3Seed crystal is placed at the bottom of the quartz tube, and then the obtained compound MgB is put5O7F3The fluxing agent is NaF: B2O3Mixing according to a molar ratio of 1: 5, wherein NaF-B2O3NaF and B in the system2O3The molar ratio of the raw materials is 1: 4, the raw materials are put into a quartz tube, the quartz tube is vacuumized, and the vacuum degree reaches 1 multiplied by 10-3Pa, vacuum packaging by using a flame gun;
then putting the mixture into a muffle furnace, raising the temperature to 400 ℃ at the speed of 40 ℃/h, and keeping the temperature constantCooling to 350 deg.C at a rate of 2 deg.C/day for 20 hr, cooling to 25 deg.C at a rate of 3 deg.C/h, and cutting quartz tube to obtain MgB with diameter of phi 5mm × 4mm × 7mm5O7F3A nonlinear optical crystal.
Example 12
Growing MgB by fluxing agent method5O7F3Crystal:
according to the reaction formula: 3Mg (BF)4)2+14H3BO3→3MgB5O7F3+5BF3↑+21H2O ↓syntheticMgB5O7F3The compound, the specific procedure was carried out according to example 1:
the compound MgB obtained is5O7F3Sealing in a hydrothermal kettle, placing in a drying oven, heating to 220 deg.C at a rate of 25 deg.C/h, holding the temperature for 30 hr, cooling to 25 deg.C at a rate of 3 deg.C/h, and opening the hydrothermal kettle to obtain MgB5O7F3Seed crystals of the crystals;
firstly MgB5O7F3The seed crystal of the crystal is placed at the bottom of a quartz tube with the diameter of 10mm, and then MgB is put in a molar ratio of 1: 55O7F3Compound and flux H3BO3Mixing, placing into a quartz tube, vacuumizing the quartz tube to a vacuum degree of 1 × 10- 3Pa, vacuum packaging by using a flame gun;
then putting the mixture into a muffle furnace, heating to 600 ℃ at the speed of 40 ℃/h, keeping the temperature for 48 hours, then cooling to 550 ℃ at the speed of 3 ℃/day, then cooling to 25 ℃ at the speed of 10 ℃/h, and cutting a quartz tube to obtain MgB with the size of phi 5mm multiplied by 6mm multiplied by 4mm5O7F3A nonlinear optical crystal.
Example 13
Growing MgB by fluxing agent method5O7F3Crystal:
according to the reaction formula: 3Mg (BF)4)2+14H3BO3→3MgB5O7F3+5BF3↑+21H2O ↓syntheticMgB5O7F3Compounds, the specific procedure was carried out according to example 2;
the compound MgB obtained is5O7F3Putting into a quartz tube with diameter of 10mm, vacuumizing the quartz tube until the vacuum degree reaches 1 × 10-3Pa, vacuum packaging with a flame gun, placing into a muffle furnace, heating to 550 deg.C at a rate of 35 deg.C/h, holding the temperature for 40 hr, cooling to 25 deg.C at a rate of 5 deg.C/h, and opening a quartz tube to obtain MgB5O7F3Seed crystals of the crystals;
the obtained MgB5O7F3Seed crystal is placed at the bottom of the quartz tube, and then the obtained compound MgB is put5O7F3The fluxing agent is NaF: B2O3Mixing according to a molar ratio of 1: 5, wherein NaF-B2O3NaF and B in the system2O3The molar ratio of the raw materials is 2: 3, the raw materials are put into a quartz tube, the quartz tube is vacuumized, and the vacuum degree reaches 1 multiplied by 10-3Pa, vacuum packaging by using a flame gun;
then putting the mixture into a muffle furnace, heating to 450 ℃ at the speed of 35 ℃/h, keeping the temperature for 36 hours, then cooling to 400 ℃ at the speed of 4 ℃/day, then cooling to 30 ℃ at the speed of 10 ℃/h, and cutting a quartz tube to obtain MgB with the size of phi 6mm multiplied by 7mm multiplied by 4mm5O7F3And (4) crystals.
Example 14
Growing MgB by fluxing agent method5O7F3Crystal:
according to the reaction formula: 3Mg (BF)4)2+14H3BO3→3MgB5O7F3+5BF3↑+21H2O ↓syntheticMgB5O7F3Compounds, the specific procedure was carried out according to example 1;
the compound MgB obtained is5O7F3Putting into a quartz tube with diameter of 10mm, vacuumizing the quartz tube until the vacuum degree reaches 1 × 10-3Pa, vacuum packaging with a flame gun, placing into a muffle furnace, heating to 550 deg.C at 40 deg.C/h, holding for 25 hr, cooling to 25 deg.C at 4 deg.C/h, and cuttingOpening a quartz tube to obtain MgB5O7F3Seed crystals of the crystals;
firstly MgB5O7F3The seed crystal of the crystal is placed at the bottom of a quartz tube with the diameter of phi 10mm, and then a compound MgB is put5O7F3With fluxing agent NaF: H3BO3Mixing according to a molar ratio of 1: 10, wherein a cosolvent NaF: H3BO3NaF and H in (1)3BO3Is put into a quartz tube with the molar ratio of 3: 5, the quartz tube is vacuumized, and the vacuum degree reaches 1 multiplied by 10-3Pa, vacuum packaging by using a flame gun;
then putting the mixture into a muffle furnace, heating to 550 ℃ at the speed of 40 ℃/h, keeping the temperature for 40 hours, then cooling to 500 ℃ at the speed of 3 ℃/day, then cooling to 25 ℃ at the speed of 8 ℃/h, and cutting a quartz tube to obtain MgB with the size of phi 9mm multiplied by 7mm multiplied by 6mm5O7F3A nonlinear optical crystal.
Example 15
Growing MgB by fluxing agent method5O7F3Crystal:
according to the reaction formula: 3Mg (BF)4)2+14H3BO3→3MgB5O7F3+5BF3↑+21H2O ↓syntheticMgB5O7F3The compound, the specific procedure was carried out according to example 1:
the compound MgB obtained is5O7F3Putting into a quartz tube with diameter of 10mm, vacuumizing the quartz tube until the vacuum degree reaches 1 × 10-3Pa, vacuum packaging with a flame gun, placing into a muffle furnace, heating to 500 deg.C at a rate of 30 deg.C/h, holding for 15 hr, cooling to 25 deg.C at a rate of 5 deg.C/h, and opening a hydrothermal kettle or quartz tube to obtain MgB5O7F3Seed crystals of the crystals;
firstly MgB5O7F3The seed crystal of the crystal is placed at the bottom of a quartz tube with the diameter of 10mm, and then MgB is put in a molar ratio of 1: 105O7F3Compound and flux B2O3Mixing, placing into a quartz tube, and vacuumizing the quartz tubeThe vacuum degree reaches 1 x 10-3Pa, vacuum packaging by using a flame gun;
then putting the mixture into a muffle furnace, heating to 500 ℃ at the speed of 40 ℃/h, keeping the temperature for 45 hours, then cooling to 450 ℃ at the speed of 3 ℃/day, then cooling to 25 ℃ at the speed of 6 ℃/h, and cutting a quartz tube to obtain MgB with the size of phi 7mm multiplied by 6mm multiplied by 4mm5O7F3A nonlinear optical crystal.
Example 16
MgB growth by Bridgman-Stockbarge method5O7F3Crystal:
according to the reaction formula: 3Mg (BF)4)2+7B2O3→3MgB5O7F3+5BF3↓ [ O ] synthetic MgB5O7F3The compound, the specific procedure was carried out according to example 1:
the compound MgB obtained is5O7F3Putting into a quartz tube with diameter of 10mm, vacuumizing the quartz tube until the vacuum degree reaches 1 × 10-3Pa, vacuum packaging with a flame gun, placing into a muffle furnace, heating to 600 deg.C at 40 deg.C/h, holding for 60 hr, cooling to 25 deg.C at 5 deg.C/h, and opening a hydrothermal kettle or quartz tube to obtain MgB5O7F3Seed crystals of the crystals;
placing the obtained seed crystal at the bottom of a platinum crucible, and then putting the obtained compound MgB5O7F3Putting the mixture into a platinum crucible;
sealing a platinum crucible, placing the crucible in a crucible descending furnace, heating to 300 ℃, preserving heat for 10 hours, adjusting the position of a container to ensure that the spontaneous nucleation temperature is reached, slowly reducing the container at the speed of 0.05mm/h, simultaneously keeping the growth temperature unchanged, reducing the temperature of the growth furnace to 25 ℃ after the growth is finished, and taking out the container to obtain the MgB with the size of phi 6mm multiplied by 5mm multiplied by 4mm5O7F3A nonlinear optical crystal.
Example 17
MgB growth by Bridgman-Stockbarge method5O7F3Crystal
According to the reaction formula: 3Mg(BF4)2+7B2O3→3MgB5O7F3+5BF3↓ [ O ] synthetic MgB5O7F3The compound, the specific procedure was carried out according to example 1:
the compound MgB obtained is5O7F3Sealing in a hydrothermal kettle, placing in a drying oven, heating to 200 deg.C at a rate of 20 deg.C/h, holding for 10 hr, cooling to 25 deg.C at a rate of 1 deg.C/h, and opening the hydrothermal kettle to obtain MgB5O7F3Seed crystals of the crystals;
placing the obtained seed crystal at the bottom of an iridium crucible, and then putting the obtained compound MgB5O7F3Putting the crucible into an iridium crucible;
sealing the iridium crucible, placing the sealed iridium crucible in a crucible descending furnace, heating to 650 ℃, preserving heat for 20 hours, adjusting the position of the iridium crucible, inoculating the iridium crucible at 350 ℃, slowly reducing the temperature of the container at the speed of 2mm/h, simultaneously slowly reducing the temperature at the speed of 3 ℃/h, after the growth is finished, reducing the temperature of the growth furnace to 25 ℃, taking out the iridium crucible, and obtaining the MgB with the size of phi 7mm multiplied by 6mm multiplied by 5mm5O7F3A nonlinear optical crystal.
Example 18
MgB growth by Bridgman-Stockbarge method5O7F3Crystal:
according to the reaction formula: 3Mg (BF)4)2+7B2O3→3MgB5O7F3+5BF3↓ [ O ] synthetic MgB5O7F3The compound, the specific procedure was carried out according to example 1:
the compound MgB obtained is5O7F3Putting into a quartz tube with diameter of 10mm, vacuumizing the quartz tube until the vacuum degree reaches 1 × 10-3Pa, vacuum packaging with a flame gun, placing into a muffle furnace, heating to 400 deg.C at a rate of 30 deg.C/h, holding the temperature for 36 hr, cooling to 25 deg.C at a rate of 3 deg.C/h, and cutting quartz tube to obtain MgB5O7F3Seed crystals of the crystals;
putting the obtained seed crystal in potteryThe bottom of a porcelain crucible, and then the compound MgB obtained5O7F3Putting into a ceramic crucible;
sealing the ceramic crucible, placing the ceramic crucible in a crucible descending furnace, heating to 450 ℃, preserving heat for 15 hours, adjusting the position of the ceramic crucible, keeping the inoculation temperature at 400 ℃, then slowly reducing the ceramic crucible at the speed of 0.5mm/h, simultaneously keeping the growth temperature unchanged, after the growth is finished, cooling the growth furnace to 25 ℃, taking out the ceramic crucible, and obtaining the MgB with the size of phi 6mm, x 8mm and x 12mm5O7F3A nonlinear optical crystal.
Example 19
MgB growth by Bridgman-Stockbarge method5O7F3Crystal
According to the reaction formula: 3Mg (BF)4)2+7B2O3→3MgB5O7F3+5BF3↓ [ O ] synthetic MgB5O7F3The compound, the specific procedure was carried out according to example 1:
the compound MgB obtained is5O7F3Sealing in a hydrothermal kettle, placing in a drying oven, heating to 200 deg.C at a rate of 20 deg.C/h, holding for 10 hr, cooling to 25 deg.C at a rate of 1 deg.C/h, and opening the hydrothermal kettle to obtain MgB5O7F3Seed crystals of the crystals;
placing the obtained seed crystal at the bottom of a quartz tube, and then putting the obtained compound MgB5O7F3Putting the mixture into a quartz tube;
the quartz tube is vacuumized, and the vacuum degree reaches 1 multiplied by 10-3Pa, sealing by using a flame gun in a vacuum packaging manner, placing the quartz tube in a crucible descending furnace, heating to 600 ℃, preserving the temperature for 20 hours, adjusting the position of the quartz tube, inoculating the quartz tube at 600 ℃, slowly reducing the quartz tube at the speed of 1mm/h, simultaneously slowly reducing the temperature at the speed of 2 ℃/h, after the growth is finished, reducing the temperature of the growth furnace to 25 ℃, and taking out the quartz tube to obtain MgB with the size of phi 7mm multiplied by 6mm multiplied by 5mm, thus obtaining the MgB5O7F3A nonlinear optical crystal.
Example 20
According to the reaction formula: 3Mg (BF)4)2+7B2O3→3MgB5O7F3+5BF3↓ [ O ] synthetic MgB5O7F3The compound, the specific procedure was carried out according to example 2:
growing MgB by solvothermal method5O7F3Crystal
The compound MgB obtained is5O7F3Sealing in a hydrothermal kettle, drying in a drying oven, heating to 150 deg.C at a rate of 20 deg.C/h, holding at constant temperature for 10 hr, cooling to 25 deg.C at a rate of 1 deg.C/h, and opening the hydrothermal kettle to obtain MgB5O7F3Seed crystals of the crystals;
placing the obtained seed crystal at the bottom of a polytetrafluoroethylene lining of a clean and pollution-free hydrothermal kettle with the volume of 23mL, and then putting the obtained compound MgB5O7F3Putting the mixture into a polytetrafluoroethylene lining;
adding deionized water as a solvent into the polytetrafluoroethylene lining, and screwing and sealing the hydrothermal kettle; placing the hydrothermal kettle in a drying oven, heating to 150 ℃ at the speed of 20 ℃/h, keeping the temperature for 24 hours, and then cooling to 130 ℃ at the speed of 2 ℃/day; then reducing the temperature to 25 ℃ at the speed of 2 ℃/h, and opening the hydrothermal kettle to obtain MgB with the size of phi 5mm multiplied by 6mm multiplied by 8mm5O7F3A nonlinear optical crystal.
Example 21
According to the reaction formula: 3Mg (BF)4)2+14H3BO3→3MgB5O7F3+5BF3↑+21H2O ↓syntheticMgB5O7F3Compounds, the specific procedure was carried out according to example 2;
growing MgB by solvothermal method5O7F3Crystal
The compound MgB obtained is5O7F3Putting the mixture into the bottom of a clean and pollution-free hydrothermal kettle with the volume of 23mL, putting the bottom into a drying box, heating the bottom to 230 ℃ at the speed of 20 ℃/h, and keeping the temperature at 10 DEGH, reducing the temperature to 25 ℃ at the speed of 1 ℃/h, and opening the hydrothermal kettle to obtain MgB5O7F3Seed crystals of the crystals;
placing the obtained seed crystal at the bottom of a polytetrafluoroethylene lining of a hydrothermal kettle, and then putting the obtained compound MgB5O7F3Putting the mixture into a polytetrafluoroethylene lining of a hydrothermal kettle;
adding 10mL of solvent which is hydrofluoric acid into a polytetrafluoroethylene lining of the hydrothermal kettle, and screwing and sealing the hydrothermal kettle; placing the hydrothermal kettle in a drying oven, heating to 200 ℃ at the speed of 20 ℃/h, keeping the temperature for 24 hours, then cooling to 100 ℃ at the speed of 2 ℃/day, then cooling to 25 ℃ at the speed of 2 ℃/h, and opening the hydrothermal kettle to obtain MgB with the size of phi 5mm multiplied by 6mm multiplied by 4mm5O7F3A nonlinear optical crystal.
Example 22
According to the reaction formula: 3Mg (BF)4)2+14H3BO3→3MgB5O7F3+5BF3↑+21H2O ↓syntheticMgB5O7F3Compounds, the specific procedure was carried out according to example 2;
growing MgB by solvothermal method5O7F3Crystal
The compound MgB obtained is5O7F3Loading into the bottom of a clean and pollution-free hydrothermal kettle with a 50mL stainless steel lining provided with a platinum sleeve, placing into a muffle furnace, heating to 300 ℃ at a speed of 30 ℃/h, keeping the temperature for 15 hours, then cooling to 25 ℃ at a speed of 2 ℃/h, opening the hydrothermal kettle to obtain MgB5O7F3Seed crystals of the crystals;
placing the obtained seed crystal at the bottom of a hydrothermal kettle with a stainless steel lining provided with a platinum sleeve, and then placing the obtained compound MgB5O7F3Putting the mixture into a hydrothermal kettle with a stainless steel lining and a platinum sleeve;
adding 50mL solvent which is deionized water into a hydrothermal kettle which is provided with a platinum sleeve and is arranged in a stainless steel lining, screwing and sealing the hydrothermal kettle, and placing the hydrothermal kettle in a horseHeating to 250 ℃ at the speed of 30 ℃/h in a muffle furnace, keeping the temperature for 24 hours, reducing the temperature to 200 ℃ at the speed of 2 ℃/day, reducing the temperature to 25 ℃ at the speed of 5 ℃/h, and opening a hydrothermal kettle to obtain MgB with the size of phi 5mm multiplied by 4mm multiplied by 3mm5O7F3A nonlinear optical crystal.
Example 23
According to the reaction formula: 3Mg (BF)4)2+14H3BO3→3MgB5O7F3+5BF3↑+21H2O ↓syntheticMgB5O7F3Compounds, the specific procedure was carried out according to example 2;
growing MgB by solvothermal method5O7F3Crystal
The compound MgB obtained is5O7F3Loading into the bottom of a clean and pollution-free hydrothermal kettle with a 23mL stainless steel lining provided with a platinum sleeve, placing into a muffle furnace, heating to 500 ℃ at a speed of 35 ℃/h, keeping the temperature for 48 hours, then cooling to 25 ℃ at a speed of 4 ℃/h, opening the hydrothermal kettle to obtain MgB5O7F3Seed crystals of the crystals;
placing the obtained seed crystal at the bottom of a hydrothermal kettle with a stainless steel lining provided with a platinum sleeve, and then placing the obtained compound MgB5O7F3Putting the mixture into a hydrothermal kettle with a stainless steel lining and a platinum sleeve;
adding 80mL of solvent which is hydrofluoric acid into a hydrothermal kettle provided with a stainless steel lining with a platinum sleeve, screwing and sealing the hydrothermal kettle, placing the hydrothermal kettle in a muffle furnace, heating to 600 ℃ at the speed of 40 ℃/h, keeping the temperature for 48 hours, reducing the temperature to 550 ℃ at the speed of 3 ℃/day, reducing the temperature to 25 ℃ at the speed of 10 ℃/h, and opening the hydrothermal kettle to obtain MgB with the size of phi 5mm multiplied by 6mm multiplied by 8mm5O7F3A nonlinear optical crystal.
Example 24
According to the reaction formula: 3Mg (BF)4)2+14H3BO3→3MgB5O7F3+5BF3↑+21H2O↑Synthesis of MgB5O7F3Compounds, the specific procedure was carried out according to example 2;
growing MgB by solvothermal method5O7F3Crystal
The compound MgB obtained is5O7F3Putting the bottom of a polytetrafluoroethylene lining of a clean and pollution-free hydrothermal kettle with the volume of 23mL into a resistance furnace, heating to 220 ℃ at the speed of 40 ℃/h, keeping the temperature for 48 hours, then cooling to 25 ℃ at the speed of 5 ℃/h, opening the hydrothermal kettle to obtain MgB5O7F3Seed crystals of the crystals;
placing the obtained seed crystal at the bottom of a polytetrafluoroethylene lining of a hydrothermal kettle, and then putting the obtained compound MgB5O7F3Putting the mixture into a polytetrafluoroethylene lining of a hydrothermal kettle;
adding 10mL of solvent which is deionized water into a polytetrafluoroethylene lining of a hydrothermal kettle, screwing and sealing the hydrothermal kettle, placing the hydrothermal kettle in a drying box, heating to 210 ℃ at the speed of 40 ℃/h, keeping the temperature for 35 hours, then reducing to 160 ℃ at the speed of 3 ℃/day, reducing to 25 ℃ at the speed of 4 ℃/day, and opening the hydrothermal kettle to obtain MgB with the size of phi 5mm multiplied by 6mm multiplied by 3mm5O7F3A nonlinear optical crystal.
Example 25
Any MgB obtained in examples 1 to 245O7F3The nonlinear optical crystal is processed in matching direction, and arranged at the position 3 as shown in figure 3, at room temperature, a Q-switched Nd-YAG laser with incident wavelength of 1064nm is used as light source, and infrared beam 2 with wavelength of 1064nm is emitted from the Q-switched Nd-YAG laser 1 and enters MgB5O7F3And (3) single crystal 3, which generates green frequency doubling light with the wavelength of 532nm and has the output intensity of 1.5-2.5 times of KDP under the same condition.
Example 26
Any MgB obtained in examples 1 to 245O7F3The nonlinear optical crystal is processed in matching directions, arranged at the position 3 as shown in figure 3, and operated at room temperature by Q-switched Nd-YAG laserA light source with incident wavelength of 532nm, which emits infrared beam 2 with wavelength of 532nm into MgB by a Q-switched Nd-YAG laser 15O7F3The single crystal 3 generates frequency-doubled light with the wavelength of 266nm, and the output intensity is about 0.4-0.6 times of that of BBO under the same condition.
Example 27
Any MgB obtained in examples 1 to 245O7F3The nonlinear optical crystal is processed in matching direction, and is arranged at the position 3 as shown in FIG. 3, at room temperature, a Q-switched Nd-YAG laser is used as light source, the incident wavelength is 355nm, infrared beam 2 with 355nm wavelength emitted by the Q-switched Nd-YAG laser 1 is emitted into MgB5O7F3The single crystal 3 can observe the output of deep ultraviolet frequency doubling light with the wavelength of 177.3 nm.

Claims (8)

1. A compound magnesium pentafluoride, which is characterized in that the chemical formula of the compound is MgB5O7F3Molecular weight is 247.351, and the preparation method adopts solid phase reaction method.
2. The process for the preparation of the compound magnesium pentafluoride borate according to claim 1, characterized by the following steps:
the Mg-containing compound is Mg (BF)4)2The compound containing B is H3BO3And B2O3The F-containing compound is Mg (BF)4)2Uniformly mixing Mg, B and F according to the mol ratio of 0.5-2: 5-7: 2-4, sealing in a hydrothermal kettle or a quartz tube, placing in a resistance furnace, heating to 200 ℃ and 650 ℃ at the speed of 10-30 ℃/h, keeping the temperature for 10-48 hours, then cooling to 25 ℃ at the speed of 1-10 ℃/h, and opening the hydrothermal kettle or the quartz tube to obtain a compound MgB5O7F3。
3. A magnesium pentafluoride non-linear optical crystal is characterized in that the chemical formula of the crystal is MgB5O7F3Molecular weight of 247.351, crystal belonging to orthorhombic system, space groupCmc21Unit cell parameter a =9.87679(15) Å，b = 8.37048(9) Å，c = 7.94544(12) Å, Z = 4，V = 656.877 (3) Å3。
4. The method for producing a magnesium pentafluoride borate nonlinear optical crystal according to claim 3, characterized in that the crystal is grown by a flux method, a Bridgman method, a room temperature solution method or a solvothermal method:
the cosolvent method is used for growing magnesium pentafluoride non-linear optical crystal crystals, and the specific operation is carried out according to the following steps:
a. the Mg-containing compound is Mg (BF)4)2The compound containing B is H3BO3And B2O3The F-containing compound is Mg (BF)4)2Uniformly mixing Mg, B and F according to the mol ratio of 0.5-2: 5-7: 2-4, sealing in a hydrothermal kettle or a quartz tube, placing in a resistance furnace, heating to 200 ℃ and 650 ℃ at the speed of 10-30 ℃/h, keeping the temperature for 10-48 hours, then cooling to 25 ℃ at the speed of 1-10 ℃/h, and opening the hydrothermal kettle or the quartz tube to obtain a compound MgB5O7F3；
b. B, mixing the compound MgB obtained in the step a5O7F3Putting into a quartz tube with diameter of 10mm, vacuumizing the quartz tube until the vacuum degree reaches 1 × 10−3Pa, vacuum packaging with a flame gun, placing into a muffle furnace, heating to 200 ℃ and 650 ℃ at a speed of 10-30 ℃/h, keeping the temperature for 12-60 hours, then cooling to 25 ℃ at a speed of 1-5 ℃/h, opening a quartz tube to obtain MgB5O7F3Seed crystals of the crystals;
c. the MgB obtained in the step b5O7F3Seed crystals are placed at the bottom of a quartz tube serving as a container, and then the compound MgB obtained in the step a is put into5O7F3The fluxing agent is NaF or NaBF4、NaF-H3BO3、NaF-B2O3、H3BO3Or B2O3Mixing at a molar ratio of 1: 1-5, placing into a quartz tube, vacuumizing the quartz tube to a vacuum degree of 1 × 10−3Pa, vacuum packaging by using a flame gun;
d. will be described in detailSealing the container in c or adding 10-100mL solvent as deionized water, sealing with anhydrous alcohol or hydrofluoric acid, placing in a resistance furnace, heating to 200 ℃. (650 ℃) at a speed of 20-40 ℃/h, keeping the temperature for 12-60 hours, cooling to 50 ℃ at a speed of 1-3 ℃/day, cooling to 25 ℃ at a speed of 1-10 ℃/h, and opening the container to obtain MgB with the size of 1-20mm5O7F3A nonlinear optical crystal;
the magnesium pentafluoride non-linear optical crystal is grown by the Bridgman-Stockbarge method, and the specific operation is carried out according to the following steps:
a. the Mg-containing compound is Mg (BF)4)2The compound containing B is H3BO3And B2O3The F-containing compound is Mg (BF)4)2Uniformly mixing Mg, B and F according to the mol ratio of 0.5-2: 5-7: 2-4, sealing in a hydrothermal kettle or a quartz tube, placing in a resistance furnace, heating to 200 ℃ and 650 ℃ at the speed of 10-30 ℃/h, keeping the temperature for 10-48 hours, then cooling to 25 ℃ at the speed of 1-10 ℃/h, and opening the hydrothermal kettle or the quartz tube to obtain a compound MgB5O7F3；
b. The compound MgB obtained is5O7F3Sealing in a hydrothermal kettle, placing in a drying oven, heating to 200 deg.C at a rate of 20 deg.C/h, holding for 10 hr, cooling to 25 deg.C at a rate of 1 deg.C/h, and opening the hydrothermal kettle to obtain MgB5O7F3Seed crystals of the crystals;
c. placing the obtained seed crystal at the bottom of an iridium crucible, and then putting the obtained compound MgB5O7F3Putting the crucible into an iridium crucible;
d. sealing an iridium crucible in a crucible descending furnace, heating to 600 ℃ for 300-5O7F3A nonlinear optical crystal;
the room temperature solution method for growing magnesium pentafluoride non-linear optical crystal crystals comprises the following steps:
a. the Mg-containing compound is Mg (BF)4)2The compound containing B is H3BO3And B2O3The F-containing compound is Mg (BF)4)2Uniformly mixing Mg, B and F according to the mol ratio of 0.5-2: 5-7: 2-4, sealing in a hydrothermal kettle or a quartz tube, placing in a resistance furnace, heating to 200 ℃ and 650 ℃ at the speed of 10-30 ℃/h, keeping the temperature for 10-48 hours, then cooling to 25 ℃ at the speed of 1-10 ℃/h, and opening the hydrothermal kettle or the quartz tube to obtain a compound MgB5O7F3；
b. B, mixing the compound MgB obtained in the step a5O7F3Sealing in a hydrothermal kettle, placing in a drying box, heating to 200 ℃./h at a rate of 10-30 ℃/h, keeping the temperature for 10-48 hours, then cooling to 25 ℃ at a rate of 1-5 ℃/h, opening the hydrothermal kettle or a quartz tube to obtain MgB5O7F3Seed crystals of the crystals;
c. b, putting the seed crystal obtained in the step b at the bottom of a clean container, and then putting the obtained compound MgB5O7F3Putting into a container;
d. adding 10-100mL of solvent deionized water, absolute ethyl alcohol or hydrofluoric acid into the container in the step c, then carrying out ultrasonic treatment to fully mix and dissolve the solvent, adjusting the pH value of the solution to 1-11, filtering the solution by using qualitative filter paper, sealing the opening by using a polyvinyl chloride film, placing the opening in a static environment without shaking, pollution and air convection, pricking a plurality of small holes on the opening to adjust the volatilization rate of the solvent in the solution, standing the solution at room temperature, and obtaining the MgB with the size of 1-20mm after the growth is finished5O7F3A nonlinear optical crystal;
the solvent thermal method is used for growing magnesium pentafluoride non-linear optical crystal crystals, and the specific operation is carried out according to the following steps:
a. the Mg-containing compound is Mg (BF)4)2The compound containing B is H3BO3And B2O3The F-containing compound is Mg (BF)4)2Uniformly mixing Mg, B and F according to the mol ratio of 0.5-2: 5-7: 2-4, sealing in a hydrothermal kettle or a quartz tube, placing in a resistance furnace, heating to 200 ℃ and 650 ℃ at the speed of 10-30 ℃/h, keeping the temperature for 10-48 hours, then cooling to 25 ℃ at the speed of 1-10 ℃/h, and opening the hydrothermal kettle or the quartz tube to obtain a compound MgB5O7F3；
b. B, mixing the compound MgB obtained in the step a5O7F3Sealing in a hydrothermal kettle, heating to 200 ℃./h at 10-30 ℃/h in a drying box, keeping the temperature for 10-48 h, cooling to 25 ℃ at 1-5 ℃/h, and opening the hydrothermal kettle or a quartz tube to obtain MgB5O7F3Seed crystals of the crystals;
c. b, putting the seed crystal obtained in the step b at the bottom of a polytetrafluoroethylene lining of a clean and pollution-free hydrothermal kettle with the volume of 23mL, and then putting the obtained compound MgB5O7F3Putting the mixture into a polytetrafluoroethylene lining;
d. adding deionized water as a solvent into the polytetrafluoroethylene lining, and screwing and sealing the hydrothermal kettle; placing the hydrothermal kettle in a drying oven, heating to 150 ℃ at the speed of 20 ℃/h, keeping the temperature for 24 hours, and then cooling to 130 ℃ at the speed of 2 ℃/day; then reducing the temperature to 25 ℃ at the speed of 2 ℃/h, and opening the hydrothermal kettle to obtain MgB5O7F3A nonlinear optical crystal.
5. The method for producing a magnesium pentafluoride borate nonlinear optical crystal according to claim 4, characterized in that the flux NaF-H in the step c of the cosolvent method3BO3NaF and H in the system3BO3The molar ratio of (A) to (B) is 1-3: 1-5; NaF-B2O3NaF and B in the system2O3The molar ratio of (A) to (B) is 1-2: 1-4.
6. Use of the magnesium pentafluoride borate nonlinear optical crystal according to claim 3 in the preparation of 2-frequency or 3-frequency or 4-frequency or 5-frequency or 6-frequency doubled harmonic light output of 1064nm fundamental frequency light output by a Nd: YAG laser.
7. Use of a magnesium pentatrifluoride pentaborate nonlinear optical crystal of claim 6 in the preparation of a crystal that produces deep ultraviolet multiplied light output below 200 nm.
8. Use of the magnesium pentatrifluoride borate nonlinear optical crystal according to claim 3 in the preparation of frequency doubling generators, upper or lower frequency converters or optical parametric oscillators.
CN202011061616.1A 2020-09-30 2020-09-30 Compound magnesium pentafluoride, magnesium pentafluoride nonlinear optical crystal, preparation method and application Pending CN112111787A (en)

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CN107841786A (en) * 2017-10-31 2018-03-27 中国科学院福建物质结构研究所 A kind of inorganic compound crystal, its preparation method and application
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