Compound lead-barium-boron-oxygen-fluorine, lead-barium-boron-oxygen-fluorine nonlinear optical crystal, preparation method and application

Abstract

The invention provides a compound lead-barium-boron-oxygen-fluorine and a lead-barium-boron-oxygen-fluorine nonlinear optical crystal as well as a preparation method and application thereof, the chemical formula of the compound is Pb1. 23Ba3. 77 (BO3) 3F, the molecular weight is 968.05, and the compound is prepared by adopting a solid-phase synthesis method or a vacuum packaging method; the chemical formula of the compound of the crystal is Pb1.23Ba3.77 (BO3) 3F, the molecular weight is 968.05, the crystal belongs to an orthorhombic system, the space group is C2221, the cell parameters are as follows: a = 10.346 (8), b = 14.759 (11), c = 7.632 (6), alpha = 90 degrees, beta = 90 degrees, gamma = 90 degrees, the unit cell volume is 1165.4 (15) 3, the frequency-doubled effect of the crystal is about 2.8 times that of KH2PO4 (KDP), the ultraviolet cut-off edge is about 280 nm, the crystal is grown by adopting a melt method, a high-temperature melt method or a vacuum packaging method, the chemical stability of the crystal is good, and the crystal is suitable for large-scale production. The crystal can be used as a short-wavelength ultraviolet nonlinear optical crystal in an all-solid-state laser.

Description

Technical Field

[0001] The present invention relates to a compound lead, barium, boron, oxygen, fluorine (Pb) 1.23 Ba 3.77 (BO3)3F and lead barium boron oxygen fluorine Pb 1.23 Ba 3.77 (BO3)3F nonlinear optical crystal, preparation method and use thereof. Background Art

[0002] Short-wavelength nonlinear optical crystals can use their frequency conversion properties to convert near-infrared, visible and other band lasers into short-wavelength lasers, and have important application value in the fields of medical treatment, communication, scientific research, etc. As we all know, the current short-wavelength nonlinear optical crystals are Chinese brand crystals KBe2BO3F2 (KBBF), BaB2O4 (BBO) and LiB3O5 (LBO), but these crystals have shortcomings such as low birefringence and difficulty in growing large-sized crystals, which limit their application to a certain extent. Therefore, the preparation and synthesis of new short-wavelength nonlinear optical crystal materials with excellent comprehensive performance is of great significance and practical value.

[0003] When designing and developing new short-wavelength nonlinear optical crystals, people hope to obtain crystals with large second-order nonlinear coefficients, wide light transmission range, short cutoff edges, and moderate birefringence. Summary of the invention

[0004] The molecular weight is 968.05 and it is made by solid phase synthesis or vacuum packaging. The chemical formula of the crystalline compound is Pb 1.23 Ba 3.77 (BO3)3F, molecular weight is 968.05, belongs to the orthorhombic system, space group is C2221, unit cell parameters are α=90°,β=90°,γ=90°, the unit cell volume is Prepared by solid phase reaction method or vacuum packaging method.

[0005] Another object of the present invention is to provide a lead barium boron oxygen fluorine Pb 1.23 Ba 3.77 (BO3)3F nonlinear optical crystal, the chemical formula of which is Pb 1.23 Ba 3.77 (BO3)3F, molecular weight is 968.05, belongs to the orthorhombic system, space group is C2221, unit cell parameters are α=90°, β=90°, γ=90°.

[0006] Another object of the present invention is to provide lead barium boron oxygen fluorine Pb 1.23 Ba 3.77The preparation method of (BO3)3F nonlinear optical crystal adopts melt method, high temperature melt method or vacuum packaging method to grow crystal.

[0007] Another object of the present invention is to provide lead barium boron oxygen fluorine Pb 1.23 Ba 3.77 Applications of (BO3)3F nonlinear optical crystals.

[0008] The present invention discloses a compound of lead barium boron oxygen fluorine, the chemical formula of which is Pb 1.23 Ba 3.77 (BO3)3F, molecular weight is 968.05, belongs to the orthorhombic system, space group is C2221, unit cell parameters are α=90°,β=90°,γ=90°, the unit cell volume is It is made by solid phase method or vacuum packaging method.

[0009] The preparation method of the compound lead barium boron oxygen fluorine adopts a solid phase synthesis method or a vacuum packaging method, and the specific operation is carried out according to the following steps:

[0010] The solid phase synthesis method is used to prepare the lead barium boron oxygen fluorine compound:

[0011] The Pb-containing compound, the Ba-containing compound, the B-containing compound and the F-containing compound are mixed uniformly in a molar ratio of Pb:Ba:B:F=1.23:3.77:3:1, put into a platinum crucible, place in a muffle furnace, heat to 700-750°C, and keep the temperature constant for 48-240 hours to obtain the compound Pb 1.23 Ba 3.77 (BO3)3F, the Pb-containing compound is PbF2, PbO, Pb(NO3)2 or PbCO3; the Ba-containing compound is Ba(NO3)2, BaF2 or BaCO3; the B-containing compound is H3BO3 or B2O3; the F-containing compound is PbF2 and BaF2;

[0012] The vacuum packaging method is used to prepare the lead barium boron oxygen fluorine compound:

[0013] The molar ratio of Pb:Ba:B:F=1.23:3.77:3:1 was used to mix the Pb-containing compound, the Ba-containing compound, the B-containing compound and the F-containing compound uniformly, and the mixture was placed in a quartz tube, and the quartz tube was evacuated to a vacuum degree of 1×10 -3 Pa, high temperature sealed and placed in a muffle furnace, heated to 650-700℃ at a rate of 5-10℃ / h, and kept at this temperature for 60-120 hours to obtain compound Pb 1.23 Ba 3.77(BO3)3F, the Pb-containing compound is PbF2, PbO, Pb(NO3)2 or PbCO3; the Ba-containing compound is Ba(NO3)2, BaF2 or BaCO3; the B-containing compound is H3BO3 or B2O3; the F-containing compound is PbF2 and BaF2.

[0014] A lead-barium-boron-oxygen-fluorine nonlinear optical crystal, the chemical formula of which is Pb 1.23 Ba 3.77 (BO3)3F, molecular weight is 968.05, belongs to the orthorhombic system, space group is C2221, unit cell parameters are α=90°,β=90°,γ=90°, the unit cell volume is

[0015] The preparation method of the lead-barium-boron-oxygen-fluorine nonlinear optical crystal adopts a melt method, a high-temperature melt method or a vacuum packaging method to grow the crystal;

[0016] The melt method for growing lead-barium-boron-oxygen-fluorine nonlinear optical crystals is specifically performed in the following steps:

[0017] a. Pb:Ba:B:F=1.23:3.77:3:1 in molar ratio. Mix the Pb-containing compound, Ba-containing compound, B-containing compound and F-containing compound evenly, put them into a platinum crucible, place them in a muffle furnace, heat them to 700-750°C, and keep the temperature constant for 48-240 hours to obtain the compound Pb. 1.23 Ba 3.77 (BO3)3F, the Pb-containing compound is PbF2, PbO, Pb(NO3)2 or PbCO3; the Ba-containing compound is Ba(NO3)2, BaF2 or BaCO3; the B-containing compound is H3BO3 or B2O3; the F-containing compound is PbF2 and BaF2;

[0018] b. Compound Pb prepared in step a 1.23 Ba 3.77 (BO3)3F is placed in a platinum crucible, placed in a muffle furnace, heated to 700-730°C, and kept at this temperature for 10-120 hours to obtain a mixed melt;

[0019] c. The mixed melt obtained in step b is slowly cooled to 650°C at a rate of 0.1-4°C / h, and then rapidly cooled to room temperature at a rate of 5-15°C / h to obtain Pb 1.23 Ba 3.77 (BO3)3F seed crystal;

[0020] d. Growing crystals in the compound melt by the Czochralski method: Fix the seed crystal obtained in step c on the seed crystal rod, place the seed crystal from the top of the mixed melt obtained in step b, apply a crystal rotation of 2-10 rpm through a crystal growth controller, pull the seed crystal at a speed of 1-15 mm / day, and cool it at a rate of 0.1-10 ° C / h. After the crystal growth stops, Pb 1.23 Ba 3.77 (BO3)3F nonlinear optical crystal;

[0021] Or use the pyrolysis method to grow crystals in the compound melt: fix the seed crystal obtained in step c on the seed crystal rod, put the seed crystal from the top of the melt obtained in step b, cool it down at a rate of 0.1-10℃ / h, let the crystal grow for 50-80 hours, slowly lift the crystal but do not leave the liquid surface to continue growing, repeat this process, and when the crystal growth stops, Pb is obtained. 1.23 Ba 3.77 (BO3)3F nonlinear optical crystal;

[0022] Or use the crucible descent method to grow crystals in the compound melt: place the seed crystal prepared in step c at the bottom of the crucible, and then place the compound Pb prepared in step a 1.23 Ba 3.77 (BO3)3F is placed in a crucible, and then the platinum crucible is sealed, the temperature of the growth furnace is raised to 680-720°C, and the temperature is kept constant for 48-240 hours, the position of the crucible is adjusted to make the seed crystal slightly melted, and then the crucible is lowered at a speed of 1-10 mm / day, and at the same time, the growth temperature is kept unchanged, or the temperature is lowered to 650°C at a rate of 2°C / h. After the growth is completed, it is quickly lowered to room temperature at a rate of 5-15°C / h to obtain Pb 1.23 Ba 3.77 (BO3)3F nonlinear optical crystal;

[0023] The high temperature melt method for growing lead barium boron oxygen fluorine nonlinear optical crystals is specifically performed in the following steps:

[0024] a. The molar ratio of Pb:Ba:B:F=1.23:3.77:3:1 is to mix the Pb-containing compound, the Ba-containing compound, the B-containing compound and the F-containing compound uniformly, put them into a platinum crucible, place them in a muffle furnace, heat them to 720-750°C, and keep the temperature constant for 48-240 hours to obtain the compound Pb 1.23 Ba 3.77 (BO3)3F polycrystalline powder, wherein the Pb-containing compound is PbF2, PbO, Pb(NO3)2 or PbCO3; the Ba-containing compound is Ba(NO3)2, BaF2 or BaCO3; the B-containing compound is H3BO3 or B2O3; the F-containing compound is PbF2 and BaF2;

[0025] b. Compound Pb obtained in step a 1.23 Ba 3.77 (BO3)3F and flux are mixed evenly in a molar ratio of 1:0.1-3, and then put into a platinum crucible, heated to 680-720°C, and kept at this temperature for 10-120 hours to obtain a mixed melt; the flux is H3BO3, B2O3 or PbO;

[0026] c. Preparation of seed crystals: Place the mixed melt obtained in step b in a single crystal furnace, slowly cool it down to 550°C at a rate of 0.1-3°C / h, and then quickly cool it down to room temperature at a rate of 5-10°C / h to obtain Pb 1.23 Ba 3.77 (BO3)3F seed crystal;

[0027] d. Growing crystals: Fix the seed crystals obtained in step c on the seed crystal rod, place the seed crystals from the top of the mixed melt obtained in step b, apply a crystal rotation of 3-15 rpm through a crystal growth controller, and cool at a rate of 0.1-3°C / h. When the crystal growth stops, Pb is obtained. 1.23 Ba 3.77 (BO3)3F nonlinear optical crystal;

[0028] The vacuum packaging method for growing lead-barium-boron-oxygen-fluorine nonlinear optical crystals is specifically performed in the following steps:

[0029] a. Pb:Ba:B:F=1.23:3.77:3:1 in molar ratio. Mix the Pb-containing compound, Ba-containing compound, B-containing compound and F-containing compound evenly, put them into a quartz tube, and evacuate the quartz tube to a vacuum degree of 1×10 -3 Pa, high temperature sealed, placed in a muffle furnace, heated to 670-700°C at a rate of 5-10°C / h, and kept at this temperature for 60-120 hours to obtain compound Pb 1.23 Ba 3.77 (BO3)3F, the Pb-containing compound is PbF2, PbO, Pb(NO3)2 or PbCO3; the Ba-containing compound is Ba(NO3)2, BaF2 or BaCO3; the B-containing compound is H3BO3 or B2O3; the F-containing compound is PbF2 and BaF2;

[0030] b. Compound Pb obtained in step a 1.23 Ba 3.77 (BO3)3F and flux were mixed evenly in a molar ratio of 1:0.1-3, placed in a quartz tube, and the quartz tube was evacuated to a vacuum degree of 1×10 -3Pa, sealed at high temperature, placed in a muffle furnace, heated to 670-700°C, kept constant for 60-120 hours, then cooled to 550°C at a rate of 1-3°C / h, and then quickly cooled to room temperature at a rate of 5-10°C / h to obtain Pb 1.23 Ba 3.77 (BO3)3F nonlinear optical crystal, wherein the flux is H3BO3, B2O3 or NH4H2PO4.

[0031] The lead-barium-boron-oxygen-fluorine nonlinear optical crystal is used in preparing the harmonic light output of the 1064nm fundamental frequency light output by the Nd:YAG laser for double frequency.

[0032] The lead-barium-boron-oxygen-fluorine nonlinear optical crystal is used in preparing ultraviolet frequency-doubled light output below 532nm.

[0033] The lead-barium-boron-oxygen-fluorine nonlinear optical crystal is used in preparing a frequency doubling generator, an up or down frequency converter or an optical parametric oscillator.

[0034] The preparation method of the lead-barium-boron-oxygen-fluorine nonlinear optical crystal described in the present invention comprises a platinum crucible, an iridium crucible, a ceramic crucible, a quartz tube, a conical flask, and a beaker. When the container is a quartz tube, it needs to be vacuumed before sealing to prevent the volatilization of the raw materials during the reaction and the explosion of the quartz tube. When the container is a conical flask or a beaker, the container must be cleaned with acid first, then rinsed with deionized water, and dried.

[0035] In the preparation method of the lead-barium-boron-oxygen-fluorine nonlinear optical crystal described in the present invention, the resistance furnace used in the preparation process is a muffle furnace or a drying box.

[0036] The preparation method of the lead-barium-boron-oxygen-fluorine nonlinear optical crystal of the present invention is adopted to obtain a Pb2O3 crystal with a size of centimeters. 1.23 Ba 3.77 (BO3)3F nonlinear optical crystal, using a large crucible or container and extending the crystal growth period, can obtain a corresponding large-sized nonlinear optical crystal Pb 1.23 Ba 3.77 (BO3)3F, in this Pb 1.23 Ba 3.77 During the growth of (BO3)3F nonlinear optical crystals, the crystals are easy to grow, transparent and without wrapping, and have the advantages of fast growth rate, low cost, and easy to obtain large-sized crystals.

[0037] The preparation method of the lead-barium-boron-oxygen-fluorine nonlinear optical crystal of the present invention is used to obtain a large-size Pb 1.23 Ba 3.77(BO3)3F nonlinear optical crystal can be used as a nonlinear optical device by orienting the crystal blank according to the crystal crystallographic data, cutting the crystal according to the required angle, thickness and cross-sectional size, and polishing the light-transmitting surface of the crystal. 1.23 Ba 3.77 (BO3)3F nonlinear optical crystal has the advantages of a light transmission band of 310nm, stable physical and chemical properties, not easy to deliquesce, easy to process and store, etc. BRIEF DESCRIPTION OF THE DRAWINGS

[0038] Figure 1 The compound Pb of the present invention 1.23 Ba 3.77 Powder XRD pattern of (BO3)3F;

[0039] Figure 2 Pb 1.23 Ba 3.77 Structure diagram of (BO3)3F crystal;

[0040] Figure 3 Pb 1.23 Ba 3.77 The working principle diagram of the nonlinear optical device made of (BO3)3F crystal, where 1 is the laser, 2 is the emitted light beam, and 3 is the Pb 1.23 Ba 3.77 (BO3)3F crystal, 4 is the outgoing beam, and 5 is the filter. DETAILED DESCRIPTION

[0041] The present invention is further described below in conjunction with the examples. It should be noted that the following examples cannot be used to limit the scope of protection of the present invention, and any improvements made on the basis of the present invention do not violate the spirit of the present invention. The raw materials or equipment used in the present invention, unless otherwise specified, are all commercially available.

[0042] Example 1

[0043] Preparation of compounds:

[0044] According to the reaction formula: 2.46PbCO3+6.54Ba(NO3)2+BaF2+6H3BO3→2Pb 1.23 Ba 3.77 (BO3)3F+13.08NO2+9H2O+3.27O2+2.46CO2, using solid phase reaction method to synthesize compound Pb 1.23 Ba 3.77 (BO3) 3F:

[0045] PbCO3, Ba(NO3)2, BaF2, and H3BO3 were mixed evenly in a molar ratio of 2.46:6.54:1:6, put into a platinum crucible, placed in a muffle furnace and heated to 730°C, and kept at this temperature for 48 hours to obtain the compound Pb 1.23 Ba 3.77 (BO3)3F.

[0046] Example 2

[0047] Preparation of compounds:

[0048] According to the reaction formula: 2.46PbO+6.54Ba(NO3)2+BaF2+6H3BO3→2Pb 1.23 Ba 3.77 (BO3)3F+13.08NO2+9H2O+3.27O2, using solid phase reaction method to synthesize compound Pb 1.23 Ba 3.77 (BO3) 3F:

[0049] PbO, Ba(NO3)2, BaF2, and H3BO3 were mixed evenly in a molar ratio of 2.46:6.54:1:6, put into a platinum crucible, placed in a muffle furnace and heated to 700°C, and kept at this temperature for 60 hours to obtain the compound Pb 1.23 Ba 3.77 (BO3)3F.

[0050] Example 3

[0051] Preparation of compounds:

[0052] According to the reaction formula: PbF2+1.46PbCO3+7.54Ba(NO3)2+6H3BO3→2Pb 1.23 Ba 3.77 (BO3)3F+1.46CO2+

[0053] 15.08NO2+9H2O+3.77O2, using solid phase reaction method to synthesize compound Pb 1.23 Ba 3.77 (BO3) 3F:

[0054] PbF2, PbCO3, Ba(NO3)2, and H3BO3 were mixed evenly in a molar ratio of 3:4:1, put into a platinum crucible, placed in a muffle furnace and heated to 720°C, and kept at this temperature for 120 hours to obtain the compound Pb 1.23 Ba 3.77 (BO3)3F.

[0055] Example 4

[0056] Preparation of compounds:

[0057] According to the reaction formula: PbF2+1.46Pb(NO3)2+7.54Ba(NO3)2+6H3BO3→2Pb 1.23 Ba 3.77 (BO3)3F+18NO2+9H2O+4.5O2, using solid phase reaction method to synthesize compound Pb 1.23 Ba 3.77 (BO3) 3F:

[0058] PbF2, Pb(NO3)2, Ba(NO3)2 and H3BO3 were mixed evenly in a molar ratio of 1:1.46:7.54:6, put into a platinum crucible, placed in a muffle furnace and heated to 710°C, and kept at this temperature for 120 hours to obtain the compound Pb 1.23 Ba 3.77 (BO3)3F.

[0059] Example 5

[0060] Preparation of compounds:

[0061] According to the reaction formula: BaF2+6.54Ba(NO3)2+2.46Pb(NO3)2+3B2O3→2Pb 1.23 Ba 3.77 (BO3)3F+18NO2+4.5O2, using solid phase reaction method to synthesize compound Pb 1.23 Ba 3.77 (BO3) 3F:

[0062] BaF2, Ba(NO3)2, Pb(NO3)2, and B2O3 were mixed evenly in a molar ratio of 1:6.54:2.46:3, placed in a platinum crucible, and heated to 685°C in a muffle furnace and kept at this temperature for 240 hours to obtain the compound Pb 1.23 Ba 3.77 (BO3)3F.

[0063] Example 6

[0064] Preparation of compounds:

[0065] According to the reaction formula: 2.46PbCO3+BaF2+6.54BaCO3+3B2O3→2Pb 1.23 Ba 3.77 (BO3)3F+9CO2, using solid phase reaction method to synthesize compound Pb 1.23 Ba 3.77 (BO3) 3F:

[0066] PbCO3, BaF2, BaCO3 and B2O3 were mixed evenly in a molar ratio of 2.46:1:6.54:3, put into a platinum crucible, placed in a muffle furnace and heated to 705°C, and kept at this temperature for 48 hours to obtain the compound Pb 1.23 Ba 3.77 (BO3)3F.

[0067] Example 7

[0068] Preparation of compounds:

[0069] According to the reaction formula: 2.46PbO+BaF2+6.54BaCO3+3B2O3→2Pb 1.23 Ba 3.77 (BO3)3F+5O2+6CO2, synthesizing compound Pb by vacuum encapsulation method 1.23 Ba 3.77 (BO3) 3F:

[0070] PbO, BaF2, BaCO3 and B2O3 were mixed evenly in a molar ratio of 2.46:1:6.54:3 and placed in a Φ40 mm quartz tube. The quartz tube was evacuated to a vacuum degree of 1×10 -3 Pa, sealed at high temperature, placed in a muffle furnace, heated to 670°C at a rate of 5°C / h, and kept at this temperature for 72 hours to obtain compound Pb 1.23 Ba 3.77 (BO3)3F.

[0071] Example 8

[0072] Preparation of compounds:

[0073] According to the reaction formula: 2.46PbO+6.54Ba(NO3)2+BaF2+3B2O3→2Pb 1.23 Ba 3.77 (BO3)3F+13.08NO2+3.27O2, synthesizing compound Pb by vacuum encapsulation method 1.23 Ba 3.77 (BO3) 3F:

[0074] PbO, Ba(NO3)2, BaF2 and B2O3 were mixed evenly in a molar ratio of 2.46:6.54:1:3, and loaded into a Φ40 mm quartz tube. The quartz tube was evacuated to a vacuum degree of 1×10 -3 Pa, sealed at high temperature, placed in a muffle furnace, heated to 710°C at a rate of 5°C / h, and kept at this temperature for 80 hours to obtain compound Pb 1.23 Ba 3.77 (BO3)3F.

[0075] Example 9

[0076] Preparation of compounds:

[0077] According to the reaction formula: 2.46PbO+BaF2+6.54BaCO3+3B2O3→2Pb 1.23 Ba 3.77 (BO3)3F+6.54CO2, synthesizing compound Pb by vacuum encapsulation method 1.23 Ba 3.77 (BO3) 3F:

[0078] PbO, BaF2, BaCO3 and B2O3 were mixed evenly in a molar ratio of 2.46:1:6.54:3 and placed in a Φ40 mm quartz tube. The quartz tube was evacuated to a vacuum degree of 1×10 -3 Pa, sealed at high temperature, placed in a muffle furnace, heated to 670°C at a rate of 8°C / h, and kept at this temperature for 100 hours to obtain compound Pb 1.23 Ba 3.77 (BO3)3F.

[0079] Example 10

[0080] Preparation of compounds:

[0081] According to the reaction formula: 1.46PbO+PbF2+7.54BaCO3+3B2O3→2Pb 1.23 Ba 3.77 (BO3)3F+7.54CO2, synthesizing compound Pb by vacuum encapsulation method 1.23 Ba 3.77 (BO3) 3F:

[0082] PbO, PbF2, BaCO3 and B2O3 were mixed evenly in a molar ratio of 1.46:1:7.54:3 and placed in a Φ40 mm quartz tube. The quartz tube was evacuated to a vacuum degree of 1×10 -3 Pa, sealed at high temperature, placed in a muffle furnace, heated to 700°C at a rate of 7°C / h, and kept at this temperature for 70 hours to obtain compound Pb 1.23 Ba 3.77 (BO3)3F.

[0083] Embodiment 11

[0084] Melt growth of Pb 1.23 Ba 3.77 (BO3)3F nonlinear optical crystal:

[0085] Compound Pb prepared according to Example 1 1.23 Ba 3.77(BO3)3F powder was loaded into a platinum crucible, placed in a muffle furnace, heated to 730°C, and kept at this temperature for 80 hours to obtain a mixed melt;

[0086] The mixed melt was slowly cooled to 650°C at a rate of 0.1°C / h, and then rapidly cooled to room temperature at a rate of 10°C / h to obtain Pb 1.23 Ba 3.77 (BO3)3F seed crystal;

[0087] The crystal was grown by the pulling method: the obtained seed crystal was fixed on the seed crystal rod, and the seed crystal was placed from the top of the mixed melt. The crystal was rotated at 4 rpm by the crystal growth controller, and the seed crystal was pulled at a speed of 1 mm / day. The temperature was lowered at a rate of 0.1 °C / h. After the crystal growth stopped, a Pb crystal with a size of 15 mm×10 mm×6 mm was obtained. 1.23 Ba 3.77 (BO3)3F nonlinear optical crystal.

[0088] Example 12

[0089] Melt growth of Pb 1.23 Ba 3.77 (BO3)3F nonlinear optical crystal:

[0090] The compound Pb prepared in Example 2 1.23 Ba 3.77 (BO3)3F was loaded into a platinum crucible, placed in a muffle furnace, heated to 720°C, and kept at this temperature for 10 hours to obtain a mixed melt;

[0091] The mixed melt was slowly cooled to 650°C at a rate of 1°C / h, and then rapidly cooled to room temperature at a rate of 5°C / h to obtain Pb 1.23 Ba 3.77 (BO3)3F seed crystal;

[0092] The crystal was grown in the compound melt by the pulling method: the obtained seed crystal was fixed on the seed crystal rod, and the seed crystal was placed from the top of the prepared mixed melt. The crystal was rotated at 2 rpm by the crystal growth controller, and the seed crystal was pulled at a speed of 4 mm / day. At the same time, the temperature was lowered at a rate of 1 °C / h. After the crystal growth stopped, a Pb crystal with a size of 11 mm × 6 mm × 2 mm was obtained. 1.23 Ba 3.77 (BO3)3F nonlinear optical crystal;

[0093] Example 13

[0094] Melt growth of Pb 1.23 Ba 3.77 (BO3)3F nonlinear optical crystal:

[0095] The compound Pb prepared in Example 3 1.23 Ba 3.77 (BO3)3F was loaded into a platinum crucible, placed in a muffle furnace, heated to 715°C, and kept at this temperature for 120 hours to obtain a mixed melt;

[0096] The mixed melt was slowly cooled to 650°C at a rate of 4°C / h, and then rapidly cooled to room temperature at a rate of 15°C / h to obtain Pb 1.23 Ba 3.77 (BO3)3F seed crystal;

[0097] The crystal was grown in the compound melt by the Czochralski method: the obtained seed crystal was fixed on the seed crystal rod, and the seed crystal was placed from the top of the prepared mixed melt. The crystal was rotated at 10 rpm by the crystal growth controller, and the seed crystal was pulled at a speed of 15 mm / day. At the same time, the temperature was lowered at a rate of 10 °C / h. After the crystal growth stopped, a Pb crystal with a size of 12 mm × 9 mm × 4 mm was obtained. 1.23 Ba 3.77 (BO3)3F nonlinear optical crystal;

[0098] Embodiment 14

[0099] Melt growth of Pb 1.23 Ba 3.77 (BO3)3F nonlinear optical crystal:

[0100] Compound Pb prepared according to Example 4 1.23 Ba 3.77 (BO3)3F powder was loaded into a platinum crucible, placed in a muffle furnace, heated to 690°C, and kept at this temperature for 120 hours to obtain a mixed melt;

[0101] The mixed melt was slowly cooled to 650°C at a rate of 1°C / h, and then rapidly cooled to room temperature at a rate of 15°C / h to obtain Pb 1.23 Ba 3.77 (BO3)3F seed crystal;

[0102] The crystal was grown by the kyberysis method: the obtained seed crystal was fixed on the seed crystal rod, and the seed crystal was placed from the top of the mixed melt. The temperature was lowered at a rate of 0.1°C / h, and the crystal was grown for 20 hours. The crystal was slowly lifted but not out of the liquid surface, and continued to grow. This was repeated 3 times to obtain a Pb crystal with a size of 6mm×10mm×8mm. 1.23 Ba 3.77 (BO3)3F nonlinear optical crystal.

[0103] Embodiment 15

[0104] Melt growth of Pb 1.23 Ba 3.77(BO3)3F nonlinear optical crystal:

[0105] The compound Pb prepared in Example 5 1.23 Ba 3.77 (BO3)3F was loaded into a platinum crucible, placed in a muffle furnace, heated to 710°C, and kept at this temperature for 100 hours to obtain a mixed melt;

[0106] The mixed melt was slowly cooled to 650°C at a rate of 0.1°C / h, and then rapidly cooled to room temperature at a rate of 5°C / h to obtain Pb 1.23 Ba 3.77 (BO3)3F seed crystal;

[0107] The crystal was grown in the compound melt by the pyrolysis method: the obtained seed crystal was fixed on the seed crystal rod, the seed crystal was placed from the top of the prepared melt, the temperature was lowered at a rate of 1°C / h, the crystal was grown for 10 hours, the crystal was slowly lifted but not separated from the liquid surface to continue growing, and this was repeated 3 times. After the crystal growth stopped, a Pb crystal with a size of 7mm×9mm×6mm was obtained. 1.23 Ba 3.77 (BO3)3F nonlinear optical crystal.

[0108] Example 16

[0109] Melt growth of Pb 1.23 Ba 3.77 (BO3)3F nonlinear optical crystal:

[0110] The compound Pb prepared in Example 6 1.23 Ba 3.77 (BO3)3F was loaded into a platinum crucible, placed in a muffle furnace, heated to 690°C, and kept at this temperature for 80 hours to obtain a mixed melt;

[0111] The mixed melt was slowly cooled to 650°C at a rate of 4°C / h, and then rapidly cooled to room temperature at a rate of 15°C / h to obtain Pb 1.23 Ba 3.77 (BO3)3F seed crystal;

[0112] The crystal was grown in the compound melt by the pyrolysis method: the obtained seed crystal was fixed on the seed crystal rod, the seed crystal was placed from the top of the prepared melt, the temperature was lowered at a rate of 10℃ / h, the crystal was grown for 30 hours, the crystal was slowly lifted but not separated from the liquid surface to continue growing, and this was repeated 3 times. After the crystal growth stopped, a Pb crystal with a size of 8mm×3mm×2mm was obtained. 1.23 Ba 3.77 (BO3)3F nonlinear optical crystal;

[0113] Embodiment 17

[0114] Melt growth of Pb 1.23 Ba 3.77 (BO3)3F nonlinear optical crystal:

[0115] Compound Pb prepared according to Example 7 1.23 Ba 3.77 (BO3)3F powder was placed in a platinum crucible, heated to 695°C, and kept at this temperature for 60 hours to obtain a mixed melt;

[0116] The mixed melt was slowly cooled to 650°C at a rate of 1.5°C / h, and then rapidly cooled to room temperature at a rate of 8°C / h to obtain Pb 1.23 Ba 3.77 (BO3)3F seed crystal;

[0117] The crystal was grown in the compound melt by the crucible descent method: the obtained seed crystal was placed at the bottom of the crucible, and the compound Pb prepared in Example 7 was then 1.23 Ba 3.77 The (BO3)3F polycrystalline powder was placed in a crucible, and then the platinum crucible was sealed. The temperature of the growth furnace was raised to 710°C and kept constant for 120 hours. The position of the crucible was adjusted to make the seed crystal slightly melted. The crucible was then lowered at a rate of 5 mm / day and cooled to 650°C at a rate of 2°C / h. After the growth was completed, the temperature was quickly cooled to room temperature at a rate of 15°C / h. Thus, a PbO2 with a size of 13 mm×8 mm×6 mm was obtained. 1.23 Ba 3.77 (BO3)3F nonlinear optical crystal.

[0118] Embodiment 18

[0119] Melt growth of Pb 1.23 Ba 3.77 (BO3)3F nonlinear optical crystal:

[0120] The compound Pb prepared in Example 4 1.23 Ba 3.77 (BO3)3F was loaded into a platinum crucible, placed in a muffle furnace, heated to 725°C, and kept at this temperature for 120 hours to obtain a mixed melt;

[0121] The mixed melt was slowly cooled to 650°C at a rate of 0.1°C / h, and then rapidly cooled to room temperature at a rate of 15°C / h to obtain Pb 1.23 Ba 3.77 (BO3)3F seed crystal;

[0122] Use the crucible descent method to grow crystals in the compound melt: place the prepared seed crystal at the bottom of the crucible, and then place the prepared compound Pb 1.23 Ba 3.77(BO3)3F was placed in a crucible, and then the platinum crucible was sealed. The temperature of the growth furnace was raised to 730°C and kept constant for 48 hours. The position of the crucible was adjusted to make the seed crystal slightly melted, and then the crucible was lowered at a rate of 1 mm / day. At the same time, the growth temperature was kept constant. After the growth was completed, the crucible was quickly lowered to room temperature at a rate of 5°C / h, and a Pb with a size of 8 mm×7 mm×8 mm was obtained. 1.23 Ba 3.77 (BO3)3F nonlinear optical crystal;

[0123] Embodiment 19

[0124] Melt growth of Pb 1.23 Ba 3.77 (BO3)3F nonlinear optical crystal:

[0125] Compound Pb prepared in Example 9 1.23 Ba 3.77 (BO3)3F was loaded into a platinum crucible, placed in a muffle furnace, heated to 730°C, and kept at this temperature for 10 hours to obtain a mixed melt;

[0126] The mixed melt was slowly cooled to 650°C at a rate of 4°C / h, and then rapidly cooled to room temperature at a rate of 5°C / h to obtain Pb 1.23 Ba 3.77 (BO3)3F seed crystal;

[0127] Use the crucible descent method to grow crystals in the compound melt: place the prepared seed crystal at the bottom of the crucible, and then place the prepared compound Pb 1.23 Ba 3.77 (BO3)3F was placed in a crucible, and then the platinum crucible was sealed. The temperature of the growth furnace was raised to 740°C and kept constant for 240 hours. The position of the crucible was adjusted to make the seed crystal slightly melted, and then the crucible was lowered at a rate of 10 mm / day. At the same time, the growth temperature was kept unchanged. After the growth was completed, the crucible was quickly lowered to room temperature at a rate of 15°C / h, and a Pb crystal with a size of 12 mm×7 mm×3 mm was obtained. 1.23 Ba 3.77 (BO3)3F nonlinear optical crystal;

[0128] Embodiment 20

[0129] Growth of Pb by high temperature melt method 1.23 Ba 3.77 (BO3)3F nonlinear optical crystal:

[0130] The compound Pb prepared in Example 6 was added in a molar ratio of 1:0.6. 1.23 Ba 3.77(BO3)3F polycrystalline powder and flux B2O3 are mixed evenly, put into a platinum crucible, heated to 680°C, and kept at this temperature for 60 hours to obtain a mixed melt;

[0131] Preparation of seed crystal: The obtained mixed melt was placed in a single crystal furnace, slowly cooled to 650°C at a rate of 0.1°C / h, and then rapidly cooled to room temperature at a rate of 5°C / h to obtain Pb 1.23 Ba 3.77 (BO3)3F seed crystal;

[0132] Growing crystals: The obtained seed crystals were fixed on the seed crystal rods, and the seed crystals were placed from above the mixed melt. The crystals were rotated at 3 rpm by the crystal growth controller, and the temperature was lowered at a rate of 0.1 °C / h. After the crystal growth stopped, a Pb crystal with a size of 12 mm × 6 mm × 2 mm was obtained. 1.23 Ba 3.77 (BO3)3F nonlinear optical crystal.

[0133] Embodiment 21

[0134] Growth of Pb by high temperature melt method 1.23 Ba 3.77 (BO3)3F nonlinear optical crystal:

[0135] The compound Pb obtained in Example 4 was added in a molar ratio of 1:1. 1.23 Ba 3.77 (BO3)3F and flux H3BO3 are mixed evenly, then put into a platinum crucible, heated to 670°C, and kept at this temperature for 10 hours to obtain a mixed melt;

[0136] Preparation of seed crystal: The obtained mixed melt was placed in a single crystal furnace, slowly cooled to 550°C at a rate of 1°C / h, and then rapidly cooled to room temperature at a rate of 8°C / h to obtain Pb 1.23 Ba 3.77 (BO3)3F seed crystal;

[0137] Growing crystals: The obtained seed crystals were fixed on the seed crystal rods, and the seed crystals were placed from the top of the prepared mixed melt. The crystals were rotated at 8 rpm by the crystal growth controller, and the temperature was lowered at a rate of 1 °C / h. After the crystal growth stopped, a Pb crystal with a size of 9 mm × 3 mm × 2 mm was obtained. 1.23 Ba 3.77 (BO3)3F nonlinear optical crystal.

[0138] Embodiment 22

[0139] Growth of Pb by high temperature melt method 1.23 Ba 3.77 (BO3)3F nonlinear optical crystal:

[0140] The compound Pb obtained in Example 8 was added in a molar ratio of 1:0.3 1.23 Ba 3.77 (BO3)3F and flux PbO are mixed evenly, then put into a platinum crucible, heated to 675°C, and kept at this temperature for 120 hours to obtain a mixed melt;

[0141] Preparation of seed crystal: The obtained mixed melt was placed in a single crystal furnace, slowly cooled to 600°C at a rate of 2°C / h, and then rapidly cooled to room temperature at a rate of 10°C / h to obtain Pb 1.23 Ba 3.77 (BO3)3F seed crystal;

[0142] Growing crystals: The obtained seed crystals were fixed on the seed crystal rods, and the seed crystals were placed from the top of the prepared mixed melt. The crystals were rotated at 10 rpm by the crystal growth controller, and the temperature was lowered at a rate of 0.5 °C / h. After the crystal growth stopped, a Pb crystal with a size of 6 mm × 2 mm × 1 mm was obtained. 1.23 Ba 3.77 (BO3)3F nonlinear optical crystal.

[0143] Embodiment 23

[0144] Growth of Pb by high temperature melt method 1.23 Ba 3.77 (BO3)3F nonlinear optical crystal:

[0145] The compound Pb obtained in Example 7 was added in a molar ratio of 1:0.4. 1.23 Ba 3.77 (BO3)3F and flux PbF2 are mixed evenly, then placed in a platinum crucible, heated to 700°C, and kept at this temperature for 100 hours to obtain a mixed melt;

[0146] Preparation of seed crystal: The obtained mixed melt was placed in a single crystal furnace, slowly cooled to 550°C at a rate of 2°C / h, and then rapidly cooled to room temperature at a rate of 7°C / h to obtain Pb 1.23 Ba 3.77 (BO3)3F seed crystal;

[0147] Growing crystals: The obtained seed crystals were fixed on the seed crystal rods, and the seed crystals were placed from the top of the prepared mixed melt. The crystals were rotated at 15 rpm by the crystal growth controller, and the temperature was lowered at a rate of 2 °C / h. After the crystal growth stopped, a Pb crystal with a size of 4 mm × 3 mm × 2 mm was obtained. 1.23 Ba 3.77 (BO3)3F nonlinear optical crystal.

[0148] Embodiment 24

[0149] Growth of Pb by vacuum encapsulation 1.23 Ba3.77 (BO3)3F nonlinear optical crystal:

[0150] The compound Pb prepared in Example 8 was added in a molar ratio of 1:0.1. 1.23 Ba 3.77 (BO3)3F and flux H3BO3 were mixed evenly and placed in a quartz tube of Φ40 mm. The quartz tube was evacuated to a vacuum degree of 1×10 -3 After high temperature sealing, it was placed in a muffle furnace, heated to 685°C, kept at this temperature for 60 hours, then cooled to 550°C at a rate of 1.5°C / h, and then quickly cooled to room temperature at a rate of 9°C / h to obtain a Pb with a size of 3mm×2mm×1mm. 1.23 Ba 3.77 (BO3)3F nonlinear optical crystal.

[0151] Embodiment 25

[0152] Growth of Pb by vacuum encapsulation 1.23 Ba 3.77 (BO3)3F nonlinear optical crystal:

[0153] The compound Pb obtained in Example 9 was added in a molar ratio of 1:0.5. 1.23 Ba 3.77 (BO3)3F and flux B2O3 were mixed evenly and placed in a Φ40 mm quartz tube. The quartz tube was evacuated to a vacuum degree of 1×10 -3 Pa, sealed at high temperature, placed in a muffle furnace, heated to 675°C, kept constant for 80 hours, then cooled to 450°C at a rate of 1°C / h, and then quickly cooled to room temperature at a rate of 5°C / h, to obtain a Pb with a size of 3mm×4mm×2mm. 1.23 Ba 3.77 (BO3)3F nonlinear optical crystal.

[0154] Embodiment 26

[0155] Growth of Pb by vacuum encapsulation 1.23 Ba 3.77 (BO3)3F nonlinear optical crystal:

[0156] The compound Pb obtained in Example 10 was added in a molar ratio of 1:1. 1.23 Ba 3.77 (BO3)3F and flux PbO were mixed evenly and placed in a Φ40 mm quartz tube. The quartz tube was evacuated to a vacuum degree of 1×10 -3Pa, sealed at high temperature, placed in a muffle furnace, heated to 690 ° C, kept constant for 100 hours, then cooled to 550 ° C at a rate of 2 ° C / h, and then quickly cooled to room temperature at a rate of 7 ° C / h, to obtain a Pb with a size of 3 mm × 2 mm × 2 mm 1.23 Ba 3.77 (BO3)3F nonlinear optical crystal.

[0157] Embodiment 27

[0158] Any Pb obtained in Examples 11-26 1.23 Ba 3.77 (BO3)3F nonlinear optical crystals are processed in matching directions and attached Figure 3 As shown in the figure, it is placed at position 3. At room temperature, a Q-switched Nd:YAG laser is used as the light source. The incident wavelength is 1064nm. The infrared beam 2 with a wavelength of 1064nm emitted by the Q-switched Nd:YAG laser 1 is injected into the Pb 1.23 Ba 3.77 (BO3)3F single crystal 3 produces green doubled frequency light with a wavelength of 532nm, and the output intensity is about 3 times that of KDP under the same conditions.

Claims

1. A compound of lead, barium, boron, oxygen and fluorine, characterized in that The chemical formula of this compound is Pb 1.23 Ba 3.77 (BO3)3F, molecular weight is 968.05, belongs to the orthorhombic system, space group is C 2221, the unit cell parameters are a =10.346(8) Å, b =14.759(11) Å, c =7.632(6) Å, α= 90°, β= 90°, γ= 90°, unit cell volume is 1165.4(15) Å 3 , made by solid phase method or vacuum packaging method.

2. A method for preparing the compound lead barium boron oxygen fluorine as claimed in claim 1, characterized in that The solid phase synthesis method or vacuum encapsulation method is used for preparation, and the specific operation is carried out according to the following steps: The solid phase synthesis method is used to prepare the lead barium boron oxygen fluorine compound: The Pb-containing compound, the Ba-containing compound, the B-containing compound and the F-containing compound are mixed uniformly in a molar ratio of Pb:Ba:B:F=1.23:3.77:3:1, put into a platinum crucible, place in a muffle furnace, heat to 700-750°C, and keep the temperature constant for 48-240 hours to obtain the compound Pb 1.23 Ba 3.77 (BO3)3F, the Pb-containing compound is PbF2, PbO, Pb(NO3)2 or PbCO3; the Ba-containing compound is Ba(NO3)2, BaF2 or BaCO3; the B-containing compound is H3BO3 or B2O3; the F-containing compound is PbF2 and BaF2; The vacuum packaging method is used to prepare the lead barium boron oxygen fluorine compound: The molar ratio of Pb:Ba:B:F=1.23:3.77:3:1 was used to mix the Pb-containing compound, the Ba-containing compound, the B-containing compound and the F-containing compound uniformly, and the mixture was placed in a quartz tube, and the quartz tube was evacuated to a vacuum degree of 1×10 −3 Pa, high temperature sealed and placed in a muffle furnace, heated to 650-700℃ at a rate of 5-10℃ / h, and kept at this temperature for 60-120 hours to obtain compound Pb 1.23 Ba 3.77 (BO3)3F, the Pb-containing compound is PbF2, PbO, Pb(NO3)2 or PbCO3; the Ba-containing compound is Ba(NO3)2, BaF2 or BaCO3; the B-containing compound is H3BO3 or B2O3; the F-containing compound is PbF2 and BaF2.

3. A lead-barium-boron-oxygen-fluorine nonlinear optical crystal, characterized in that The chemical formula of this crystal is Pb 1.23 Ba 3.77 (BO3)3F, 968.05, belongs to the orthorhombic system, and the space group is C 2221, the unit cell parameters are a =10.346(8) Å, b =14.759(11) Å, c =7.632(6) Å, α= 90°, β= 90°, γ= 90°, unit cell volume is 1165.4(15) Å 3 .

4. A method for preparing a lead-barium-boron-oxygen-fluorine nonlinear optical crystal as claimed in claim 3, characterized in that Crystals are grown using melt method, high temperature melt method or vacuum packaging method; The melt method for growing lead-barium-boron-oxygen-fluorine nonlinear optical crystals is specifically performed in the following steps: a. Pb:Ba:B:F=1.23:3.77:3:1 in molar ratio. Mix the Pb-containing compound, Ba-containing compound, B-containing compound and F-containing compound evenly, put them into a platinum crucible, place them in a muffle furnace, heat them to 700-750°C, and keep the temperature constant for 48-240 hours to obtain the compound Pb. 1.23 Ba 3.77 (BO3)3F, the Pb-containing compound is PbF2, PbO, Pb(NO3)2 or PbCO3; the Ba-containing compound is Ba(NO3)2, BaF2 or BaCO3; the B-containing compound is H3BO3 or B2O3; the F-containing compound is PbF2 and BaF2; b. Compound Pb prepared in step a 1.23 Ba 3.77 (BO3)3F is loaded into a platinum crucible, placed in a muffle furnace, heated to 740-780°C, and kept at this temperature for 10-120 hours to obtain a mixed melt; c. The mixed melt obtained in step b is slowly cooled to 660°C at a rate of 0.1-4°C / h, and then rapidly cooled to room temperature at a rate of 5-15°C / h to obtain Pb 1.23 Ba 3.77 (BO3)3F seed crystal; d. Growing crystals in the compound melt by the Czochralski method: Fix the seed crystal obtained in step c on the seed crystal rod, place the seed crystal from the top of the mixed melt obtained in step b, apply a crystal rotation of 2-10 rpm through a crystal growth controller, pull the seed crystal at a speed of 1-15 mm / day, and cool it at a rate of 0.1-10 ° C / h. After the crystal growth stops, Pb 1.23 Ba 3.77 (BO3)3F nonlinear optical crystal; Or use the pyrolysis method to grow crystals in the compound melt: fix the seed crystal obtained in step c on the seed crystal rod, put the seed crystal from the top of the melt obtained in step b, cool it down at a rate of 0.1-10℃ / h, let the crystal grow for 50-80 hours, slowly lift the crystal but do not leave the liquid surface to continue growing, repeat this process, and when the crystal growth stops, Pb is obtained. 1.23 Ba 3.77 (BO3)3F nonlinear optical crystal; Or use the crucible descent method to grow crystals in the compound melt: place the seed crystal prepared in step c at the bottom of the crucible, and then place the compound Pb prepared in step a 1.23 Ba 3.77 (BO3)3F is placed in a crucible, and then the platinum crucible is sealed, the temperature of the growth furnace is raised to 680-720°C, and the temperature is kept constant for 48-240 hours. The position of the crucible is adjusted to make the seed crystal slightly melted, and then the crucible is lowered at a rate of 1-10 mm / day. At the same time, the growth temperature is kept unchanged, or the temperature is lowered to 650°C at a rate of 2°C / h. After the growth is completed, it is quickly lowered to room temperature at a rate of 5-15°C / h to obtain Pb 1.23 Ba 3.77 (BO3)3F nonlinear optical crystal; The high temperature melt method for growing lead barium boron oxygen fluorine nonlinear optical crystals is specifically performed in the following steps: a. Pb:Ba:B:F=1.23:3.77:3:1 in molar ratio. Mix the Pb-containing compound, the Ba-containing compound, the B-containing compound and the F-containing compound evenly, put them into a platinum crucible, place them in a muffle furnace, heat them to 690-730°C, and keep them at this temperature for 48-240 hours to obtain the compound Pb. 1.23 Ba 3.77 (BO3)3F polycrystalline powder, wherein the Pb-containing compound is PbF2, PbO, Pb(NO3)2 or PbCO3; the Ba-containing compound is Ba(NO3)2, BaF2 or BaCO3; the B-containing compound is H3BO3 or B2O3; the F-containing compound is PbF2 and BaF2; b. Compound Pb obtained in step a 1.23 Ba 3.77 (BO3)3F and flux are mixed evenly in a molar ratio of 1:0.1-3, and then put into a platinum crucible, heated to 650-700°C, and kept at this temperature for 10-120 hours to obtain a mixed melt; the flux is H3BO3, B2O3 or PbO; c. Preparation of seed crystals: Place the mixed melt obtained in step b in a single crystal furnace, slowly cool it to 600°C at a rate of 0.1-3°C / h, and then quickly cool it to room temperature at a rate of 5-10°C / h to obtain Pb 1.23 Ba 3.77 (BO3)3F seed crystal; d. Growing crystals: Fix the seed crystals obtained in step c on the seed crystal rod, place the seed crystals from the top of the mixed melt obtained in step b, apply a crystal rotation of 3-15 rpm through a crystal growth controller, and cool at a rate of 0.1-3°C / h. When the crystal growth stops, Pb is obtained. 1.23 Ba 3.77 (BO3)3F nonlinear optical crystal; The vacuum packaging method for growing lead-barium-boron-oxygen-fluorine nonlinear optical crystals is specifically performed in the following steps: a. Pb:Ba:B:F=1.23:3.77:3:1 in molar ratio. Mix the Pb-containing compound, Ba-containing compound, B-containing compound and F-containing compound evenly, put them into a quartz tube, and evacuate the quartz tube to a vacuum degree of 1×10 −3 Pa, high temperature sealed, placed in a muffle furnace, heated to 650-700°C at a rate of 5-10°C / h, and kept at this temperature for 60-120 hours to obtain compound Pb 1.23 Ba 3.77 (BO3)3F, the Pb-containing compound is PbF2, PbO, Pb(NO3)2 or PbCO3; the Ba-containing compound is Ba(NO3)2, BaF2 or BaCO3; the B-containing compound is H3BO3 or B2O3; the F-containing compound is PbF2 and BaF2; b. Compound Pb obtained in step a 1.23 Ba 3.77 (BO3)3F and flux were mixed evenly in a molar ratio of 1:0.1-3, placed in a quartz tube, and the quartz tube was evacuated to a vacuum degree of 1×10 −3 Pa, sealed at high temperature, placed in a muffle furnace, heated to 650-670°C, kept constant for 60-120 hours, then cooled to 550°C at a rate of 1-3°C / h, and then quickly cooled to room temperature at a rate of 5-10°C / h to obtain Pb 1.23 Ba 3.77 (BO3)3F nonlinear optical crystal, wherein the flux is H3BO3, B2O3 or PbO.

5. A use of the lead-barium-boron-oxygen-fluorine nonlinear optical crystal as claimed in claim 3 in preparing a harmonic light output of the 1064nm fundamental frequency light output by a Nd:YAG laser for double frequency.

6. Use of the lead-barium-boron-oxygen-fluorine nonlinear optical crystal as claimed in claim 5 in the preparation of ultraviolet frequency-doubled light output below 532 nm.

7. Use of the lead-barium-boron-oxygen-fluorine nonlinear optical crystal as claimed in claim 3 in the preparation of a frequency doubling generator, an up or down frequency converter or an optical parametric oscillator.

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