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

Abstract

The invention provides a compound lead-barium-boron-nitrogen-oxygen and a lead-barium-boron-nitrogen-oxygen nonlinear optical crystal as well as a preparation method and application thereof, the chemical formula of the compound is Pb2Ba3 (BO3) 3 (NO3), the molecular weight is 1039.98, 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 Pb2Ba3 (BO3) 3 (NO3), the molecular weight is 1039.98, the crystal belongs to an orthorhombic system, the space group is C2221, the cell parameters are as follows: a = 10.4818 (5), b = 14.4102 (7), c = 8.0332 (4), alpha = 90 degrees, beta = 90 degrees, gamma = 90 degrees, the unit cell volume is 1213.37 (10) 3, the frequency-doubled effect of the crystal is about 3.2 times that of KH2PO4 (KDP), the ultraviolet cut-off edge is about 320 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 industrial 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 nitrogen oxygen Pb 2 Ba 3 (BO 3 ) 3 (NO 3 ) and lead barium boron nitrogen oxygen Pb 2 Ba 3 (BO 3 ) 3 (NO 3 )Nonlinear optical crystals and their preparation methods and uses. 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, which have important application value in the fields of medicine, communication, scientific research, etc. As we all know, the current short-wavelength nonlinear optical crystal is crystal KBe 2 BO 3 F 2 (KBBF), BaB 2 O 4 (BBO) and LiB 3 O 5 (LBO), etc., 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 edge, and moderate birefringence. However, in some known compounds, the balance between frequency doubling, band gap, and birefringence cannot be achieved. For example, Ba 5 (BO 3 ) 3 Cl, this compound has a shorter UV cutoff edge, but the frequency-doubling effect is only 0.5 times that of KDP. By replacing Ba with Pb ions containing lone pairs of electrons, the frequency-doubling effect is significantly improved, but the birefringence is still not improved. Therefore, considering that without affecting the frequency doubling, how to improve its birefringence so that it can be used in a shorter wavelength range is a current research hotspot. 3 The group has the same valence as the halogen ion. If the halogen atom in its compound is replaced by NO with larger anisotropy 3 group, it is beneficial to obtain a larger birefringence. Summary of the invention

[0004] The present invention provides a lead-barium-boron-nitrogen-oxygen compound and a lead-barium-boron-nitrogen-oxygen nonlinear optical crystal and a preparation method and use thereof. The chemical formula of the compound is Pb 2 Ba 3 (BO 3 ) 3 (NO 3 ), molecular weight 1039.98, made by solid phase synthesis or vacuum packaging; the chemical formula of the crystalline compound is Pb 2 Ba 3 (BO 3 ) 3 (NO 3 ), molecular weight is 1039.98, belongs to orthorhombic system, space group is C222 1 , the 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 nitrogen oxide Pb 2 Ba 3 (BO 3 ) 3 (NO 3 ) nonlinear optical crystal, the chemical formula of which is Pb 2 Ba 3 (BO 3 ) 3 (NO 3 ), molecular weight is 1039.98, belongs to orthorhombic system, space group is C222 1 , the unit cell parameters are α=90°, β=90°, γ=90°.

[0006] Another object of the present invention is to provide lead barium boron nitrogen oxide Pb 2 Ba 3 (BO 3 ) 3 (NO 3 ) A method for preparing nonlinear optical crystals, using a melt method, a high-temperature melt method or a vacuum packaging method to grow crystals.

[0007] Another object of the present invention is to provide lead barium boron nitrogen oxide Pb 2 Ba 3 (BO 3 ) 3 (NO 3 )Applications of nonlinear optical crystals.

[0008] The present invention discloses a compound of lead, barium, boron, nitrogen and oxygen, the chemical formula of which is Pb 2Ba 3 (BO 3 ) 3 (NO 3 ), molecular weight is 1039.98, belongs to orthorhombic system, space group is C222 1 , the 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 lead barium boron nitrogen oxygen compound 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 nitrogen oxide compound:

[0011] The Pb-containing compound, the Ba-containing compound, the B-containing compound and the N-containing compound are mixed uniformly in a molar ratio of Pb:Ba:B:N=2:3:3:1, put into a platinum crucible, place in a muffle furnace, heat to 500-600°C, and keep the temperature constant for 48-120 hours to obtain the compound Pb 2 Ba 3 (BO 3 ) 3 (NO 3 ), the Pb-containing compound is PbF 2 、PbO、Pb(NO 3 ) 2 or PbCO 3 ; Ba-containing compounds are Ba(NO 3 ) 2 , BaF 2 or BaCO 3 ; Compounds containing B are H 3 BO 3 or B 2 O 3 ; The N-containing compound is PbF 2 andBaF 2 ;

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

[0013] The Pb-containing compound, the Ba-containing compound, the B-containing compound and the N-containing compound are mixed evenly in a molar ratio of Pb:Ba:B:N=2:3:3:1, and the mixture is placed in a quartz tube. The quartz tube is evacuated to a vacuum degree of 1×10 -3 Pa, high temperature sealed and placed in a muffle furnace, heated to 450-550°C at a rate of 5-10°C / h, and kept at this temperature for 60-240 hours to obtain compound Pb 2 Ba 3(BO 3 ) 3 (NO 3 ), the Pb-containing compound is PbF 2 、PbO、Pb(NO 3 ) 2 or PbCO 3 ; Ba-containing compounds are Ba(NO 3 ) 2 , BaF 2 or BaCO 3 ; Compounds containing B are H 3 BO 3 or B 2 O 3 ; The N-containing compound is Ba(NO 3 ) 2 and Pb(NO 3 ) 2 .

[0014] A lead-barium-boron-nitrogen-oxygen nonlinear optical crystal, the chemical formula of which is Pb 2 Ba 3 (BO 3 ) 3 (NO 3 ), molecular weight is 968.05, belongs to the orthorhombic system, space group is C222 1 , the unit cell parameters are α=90°,β=90°,γ=90°, the unit cell volume is

[0015] The preparation method of the lead-barium-boron-nitrogen-oxygen 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-nitrogen-oxygen nonlinear optical crystals is specifically performed in the following steps:

[0017] a. Pb:Ba:B:N=2:3:3:1 in molar ratio. Mix the Pb-containing compound, Ba-containing compound, B-containing compound and N-containing compound evenly, put them into a platinum crucible, place them in a muffle furnace, heat them to 500-600°C, and keep them at this temperature for 48-120 hours to obtain the compound Pb. 2 Ba 3 (BO 3 ) 3 (NO 3 ), the Pb-containing compound is PbF 2 、PbO、Pb(NO 3 ) 2 or PbCO 3 ; Ba-containing compounds are Ba(NO3 ) 2 , BaF 2 or BaCO 3 ; Compounds containing B are H 3 BO 3 or B 2 O 3 ; The N-containing compound is Ba(NO 3 ) 2 and Pb(NO 3 ) 2 ;

[0018] b. Compound Pb prepared in step a 2 Ba 3 (BO 3 ) 3 (NO 3 ) is loaded into a platinum crucible, placed in a muffle furnace, heated to 550-600° 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 500°C at a rate of 0.1-4°C / h, and then rapidly cooled to room temperature at a rate of 5-20°C / h to obtain Pb 2 Ba 3 (BO 3 ) 3 (NO 3 ) 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 2-8 rpm through a crystal growth controller, pull the seed crystal at a speed of 1-10 mm / day, and cool it at a rate of 0.1-10 ° C / h. After the crystal growth stops, Pb 2 Ba 3 (BO 3 ) 3 (NO 3 ) Nonlinear optical crystals;

[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 50-100 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. 2 Ba 3 (BO 3 ) 3 (NO 3 ) Nonlinear optical crystals;

[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 2 Ba 3 (BO 3 ) 3 (NO 3 ) is placed in a crucible, and then the platinum crucible is sealed, the temperature of the growth furnace is raised to 550-580°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 1-15 mm / day, and at the same time, the growth temperature is kept unchanged, or the temperature is lowered to 500°C at a cooling rate of 1.5°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 2 Ba 3 (BO 3 ) 3 (NO 3 ) Nonlinear optical crystals;

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

[0024] a. Pb:Ba:B:N=2:3:3:1 in molar ratio. Mix the Pb-containing compound, Ba-containing compound, B-containing compound and N-containing compound evenly, put them into a platinum crucible, place them in a muffle furnace, heat them to 540-570°C, and keep the temperature constant for 48-100 hours to obtain the compound Pb 2 Ba 3 (BO 3 ) 3 (NO 3 ) polycrystalline powder, wherein the Pb-containing compound is PbF 2 、PbO、Pb(NO 3 ) 2 or PbCO 3 ; Ba-containing compounds are Ba(NO 3 ) 2 , BaF 2 or BaCO 3 ; Compounds containing B are H 3 BO 3 or B 2 O 3 ; The N-containing compound is Ba(NO 3 ) 2 and Pb(NO 3 ) 2 ;

[0025] b. Compound Pb obtained in step a 2 Ba 3 (BO 3 ) 3(NO 3 ) and flux in a molar ratio of 1:0.1-3 are mixed evenly, and then placed in 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 H 3 BO 3 , B 2 O 3 or PbO;

[0026] c. Preparation of seed crystals: Place the mixed melt obtained in step b in a single crystal furnace, slowly cool it to 500°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 2 Ba 3 (BO 3 ) 3 (NO 3 ) 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 3-8 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. 2 Ba 3 (BO 3 ) 3 (NO 3 ) Nonlinear optical crystals;

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

[0029] a. Pb:Ba:B:N=2:3:3:1 in molar ratio. Mix the Pb-containing compound, Ba-containing compound, B-containing compound and N-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 450-550°C at a rate of 5-10°C / h, and kept at this temperature for 60-150 hours to obtain compound Pb 2 Ba 3 (BO 3 ) 3 (NO 3 ), the Pb-containing compound is PbF 2 、PbO、Pb(NO 3 ) 2 or PbCO 3 ; Ba-containing compounds are Ba(NO 3 ) 2 , BaF 2 or BaCO 3 ; Compounds containing B are H3 BO 3 or B 2 O 3 ; The N-containing compound is Ba(NO 3 ) 2 and Pb(NO 3 ) 2 ;

[0030] b. Compound Pb obtained in step a 2 Ba 3 (BO 3 ) 3 (NO 3 ) and flux in a molar ratio of 1:0.1-3 are mixed evenly, placed in a quartz tube, and the quartz tube is evacuated to a vacuum degree of 1×10 -3 Pa, sealed at high temperature, placed in a muffle furnace, heated to 450-550°C, kept constant for 60-100 hours, then cooled to 400°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 2 Ba 3 (BO 3 ) 3 (NO 3 ) nonlinear optical crystal, the flux is H 3 BO 3 , B 2 O 3 or PbO.

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

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

[0033] The lead-barium-boron-nitrogen-oxygen 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-nitrogen-oxygen nonlinear optical crystal described in the present invention uses a platinum crucible, an iridium crucible, a ceramic crucible, a quartz tube, a conical flask, and a beaker as the container in the preparation process. 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-nitrogen-oxygen 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-nitrogen-oxygen nonlinear optical crystal of the present invention is adopted to obtain a Pb-barium-boron-nitrogen-oxygen nonlinear optical crystal with a size of centimeters. 2 Ba 3 (BO 3 ) 3 (NO 3 ) nonlinear optical crystal, use a large crucible or container, and extend the crystal growth period, then you can get a corresponding large-sized nonlinear optical crystal Pb 2 Ba 3 (BO 3 ) 3 (NO 3 ), in which Pb 2 Ba 3 (BO 3 ) 3 (NO 3 ) During the growth of 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-size crystals.

[0037] The preparation method of the lead-barium-boron-nitrogen-oxygen nonlinear optical crystal of the present invention can obtain a large-size Pb 2 Ba 3 (BO 3 ) 3 (NO 3 ) nonlinear optical crystal, according to the crystallographic data of the crystal, the crystal blank is oriented, the crystal is cut according to the required angle, thickness and cross-sectional size, and the light-transmitting surface of the crystal is polished, and it can be used as a nonlinear optical device. 2 Ba 3 (BO 3 ) 3 (NO 3 ) Nonlinear optical crystals have the advantages of a light transmission band of 330nm, 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 2 Ba 3 (BO 3 ) 3 (NO 3 ) powder XRD spectrum;

[0039] Figure 2 Pb 2 Ba 3 (BO 3 ) 3 (NO 3 ) Crystal structure diagram;

[0040] Figure 3 Pb 2 Ba 3 (BO 3 ) 3 (NO 3 ) The working principle diagram of the nonlinear optical device made of crystal, where 1 is the laser, 2 is the emitted light beam, and 3 is the Pb 2 Ba 3 (BO 3 ) 3 (NO 3 ) crystal, 4 is the outgoing light 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 commercially available.

[0042] Example 1

[0043] Preparation of compounds:

[0044] According to the reaction formula: 2PbO+3Ba(NO 3 ) 2 +3H 3 BO 3 →Pb 2 Ba 3 (BO 3 ) 3 (NO 3 )+5NO 2 +4.5H 2 O+2.25O 2 , using solid phase reaction method to synthesize compound Pb 2 Ba 3 (BO 3 ) 3 (NO 3 ):

[0045] PbO, Ba(NO 3 ) 2 and H 3 BO 3 The mixture was mixed evenly, placed in a platinum crucible, and placed in a muffle furnace and heated to 560°C. The temperature was kept constant for 60 hours to obtain compound Pb 2 Ba 3 (BO 3 ) 3 (NO 3 ).

[0046] Example 2

[0047] Preparation of compounds:

[0048] According to the reaction formula: 2PbO+0.5Ba(NO 3 ) 2 +2.5BaCO 3 +3H 3 BO 3 →Pb 2 Ba 3 (BO 3 ) 3 (NO 3 )+2.5CO 2 +4.5H 2 O, using solid phase reaction method to synthesize compound Pb 2 Ba 3 (BO 3 ) 3 (NO 3 ):

[0049] PbO, Ba(NO 3 ) 2 , BaCO 3 and H 3 BO 3 The mixture was mixed evenly, placed in a platinum crucible, and placed in a muffle furnace and heated to 520°C. The temperature was kept constant for 60 hours to obtain compound Pb 2 Ba 3 (BO 3 ) 3 (NO 3 ).

[0050] Example 3

[0051] Preparation of compounds:

[0052] According to the reaction formula: 2PbF 2 +2.5BaCO 3 +0.5Ba(NO 3 ) 2 +3H 3 BO 3 →Pb 2 Ba 3 (BO 3 ) 3 (NO 3 )+2.5CO 2 +4HF+2.5H 2 O+1.5O 2 , using solid phase reaction method to synthesize compound Pb 2 Ba 3(BO 3 ) 3 (NO 3 ):

[0053] PbF was added in a molar ratio of 2:2.5:0.5:3 2 , BaCO 3 ,Ba(NO 3 ) 2 , and H 3 BO 3 The mixture was mixed evenly, placed in a platinum crucible, and placed in a muffle furnace and heated to 510°C. The temperature was kept constant for 80 hours to obtain compound Pb 2 Ba 3 (BO 3 ) 3 (NO 3 ).

[0054] Example 4

[0055] Preparation of compounds:

[0056] According to the reaction formula: 1.5PbF 2 +0.5Pb(NO 3 ) 2 +3BaCO 3 +3H 3 BO 3 →Pb 2 Ba 3 (BO 3 ) 3 (NO 3 )+3CO 2 +3HF+3H 2 O, using solid phase reaction method to synthesize compound Pb 2 Ba 3 (BO 3 ) 3 (NO 3 ):

[0057] PbF was mixed in a molar ratio of 1.5:0.5:3:3 2 , Pb(NO 3 ) 2 , BaCO 3 and H 3 BO 3 Mix well, put into platinum crucible, place in muffle furnace and heat to 515℃, keep constant temperature for 80 hours, and then obtain compound Pb 2 Ba 3 (BO 3 ) 3 (NO 3 ).

[0058] Example 5

[0059] Preparation of compounds:

[0060] According to the reaction formula: 2.5BaF 2 +0.5Ba(NO 3 ) 2 +2PbCO 3 +3H 3 BO 3 →Pb 2 Ba 3 (BO 3 ) 3 (NO 3 )+2CO 2 +5HF+2H 2 O, using solid phase reaction method to synthesize compound Pb 2 Ba 3 (BO 3 ) 3 (NO 3 ):

[0061] BaF 2 ,Ba(NO 3 ) 2 , PbCO 3 , H 3 BO 3 The mixture was mixed evenly in a molar ratio of 2.5:0.5:2:3, placed in a platinum crucible, and placed in a muffle furnace and heated to 485°C for 240 hours to obtain compound Pb 2 Ba 3 (BO 3 ) 3 (NO 3 ).

[0062] Example 6

[0063] Preparation of compounds:

[0064] According to the reaction formula: 2PbCO 3 +0.5Ba(NO 3 ) 2 +2.5BaCO 3 +1.5B 2 O 3 →Pb 2 Ba 3 (BO 3 ) 3 (NO 3 )+4.5CO 2 , using solid phase reaction method to synthesize compound Pb 2 Ba 3 (BO 3 ) 3(NO 3 ):

[0065] PbCO was added in a molar ratio of 2:0.5:2.5:1.5 3 ,Ba(NO 3 ) 2 , BaCO 3 and B 2 O 3 Mix well, put into platinum crucible, place in muffle furnace and heat to 525℃, keep constant temperature for 60 hours, and then obtain compound Pb 2 Ba 3 (BO 3 ) 3 (NO 3 ).

[0066] Example 7

[0067] Preparation of compounds:

[0068] According to the reaction formula: 2PbO+0.5Ba(NO 3 ) 2 +2.5BaCO 3 +1.5B 2 O 3 →Pb 2 Ba 3 (BO 3 ) 3 (NO 3 )+2.5CO 2 , using vacuum packaging method to synthesize compound Pb 2 Ba 3 (BO 3 ) 3 (NO 3 ):

[0069] PbO, Ba(NO 3 ) 2 , BaCO 3 and B 2 O 3 Mix well, put into a Φ40mm quartz tube, and evacuate the quartz tube to a vacuum degree of 1×10 -3 Pa, sealed at high temperature, placed in a muffle furnace, heated to 470°C at a rate of 5°C / h, and kept at this temperature for 50 hours to obtain compound Pb 2 Ba 3 (BO 3 ) 3 (NO 3 ).

[0070] Example 8

[0071] Preparation of compounds:

[0072] According to the reaction formula: 2PbF 2 +0.5Ba(NO 3 ) 2 +2.5BaF 2 +3B 2 O 3 →Pb 2 Ba 3 (BO 3 ) 3 (NO 3 )+3BF 3 , using vacuum packaging method to synthesize compound Pb 2 Ba 3 (BO 3 ) 3 (NO 3 ):

[0073] PbO, Ba(NO 3 ) 2 , BaF 2 and B 2 O 3 Mix well, put into a Φ40mm quartz tube, and evacuate the quartz tube to a vacuum degree of 1×10 -3 Pa, sealed at high temperature, placed in a muffle furnace, heated to 510°C at a rate of 5°C / h, and kept at this temperature for 80 hours to obtain compound Pb 2 Ba 3 (BO 3 ) 3 (NO 3 ).

[0074] Example 9

[0075] Preparation of compounds:

[0076] According to the reaction formula: 2PbCO 3 +3Ba(NO 3 ) 2 +1.5B 2 O 3 →Pb 2 Ba 3 (BO 3 ) 3 (NO 3 )+2CO 2 +5NO 2 +3.5O 2 , using vacuum packaging method to synthesize compound Pb 2 Ba 3 (BO 3 )3 (NO 3 ):

[0077] PbCO was added at a molar ratio of 2:3:1.5 3 ,Ba(NO 3 ) 2 and B 2 O 3 Mix well, put into a Φ40mm quartz tube, and evacuate the quartz tube to a vacuum degree of 1×10 -3 Pa, sealed at high temperature, placed in a muffle furnace, heated to 490°C at a rate of 8°C / h, and kept at this temperature for 100 hours to obtain compound Pb 2 Ba 3 (BO 3 ) 3 (NO 3 ).

[0078] Example 10

[0079] Preparation of compounds:

[0080] According to the reaction formula: 1.5Pb0+0.5Pb(NO 3 ) 2 +3BaCO 3 +1.5B 2 O 3 →Pb 2 Ba 3 (BO 3 ) 3 (NO 3 )+3CO 2 , using vacuum packaging method to synthesize compound Pb 2 Ba 3 (BO 3 ) 3 (NO 3 ):

[0081] PbO, Pb(NO 3 ) 2 , BaCO 3 and B 2 O 3 Mix well, put into a Φ40mm quartz tube, and evacuate the quartz tube to a vacuum degree of 1×10 -3 Pa, sealed at high temperature, placed in a muffle furnace, heated to 470°C at a rate of 7°C / h, and kept at this temperature for 70 hours to obtain compound Pb 2 Ba 3 (BO 3 ) 3 (NO 3 ).

[0082] Embodiment 11

[0083] Melt growth of Pb 2 Ba 3 (BO 3 ) 3 (NO 3 ) Nonlinear optical crystals:

[0084] Compound Pb prepared according to Example 1 2 Ba 3 (BO 3 ) 3 (NO 3 ) The powder was loaded into a platinum crucible, placed in a muffle furnace, heated to 530° C., and kept at this temperature for 60 hours to obtain a mixed melt;

[0085] The mixed melt was slowly cooled to 430°C at a rate of 0.1°C / h, and then rapidly cooled to room temperature at a rate of 12°C / h to obtain Pb 2 Ba 3 (BO 3 ) 3 (NO 3 ) seed crystal;

[0086] 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 6 rpm by the crystal growth controller, and the seed crystal was pulled at a speed of 0.5 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 12 mm×10 mm×6 mm was obtained. 2 Ba 3 (BO 3 ) 3 (NO 3 )Nonlinear optical crystals.

[0087] Example 12

[0088] Melt growth of Pb 2 Ba 3 (BO 3 ) 3 (NO 3 ) Nonlinear optical crystals:

[0089] The compound Pb prepared in Example 2 2 Ba 3 (BO 3 ) 3 (NO 3 ) was loaded into a platinum crucible, placed in a muffle furnace, heated to 520° C., and kept at this temperature for 15 hours to obtain a mixed melt;

[0090] The obtained mixed melt was slowly cooled to 420°C at a rate of 1°C / h, and then rapidly cooled to room temperature at a rate of 3°C / h to obtain Pb 2 Ba 3 (BO 3 ) 3 (NO 3 ) seed crystal;

[0091] 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 4 rpm by the crystal growth controller, and the seed crystal was pulled at a speed of 2 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 × 4 mm × 3 mm was obtained. 2 Ba 3 (BO 3 ) 3 (NO 3 ) Nonlinear optical crystals;

[0092] Example 13

[0093] Melt growth of Pb 2 Ba 3 (BO 3 ) 3 (NO 3 ) Nonlinear optical crystals:

[0094] The compound Pb prepared in Example 3 2 Ba 3 (BO 3 ) 3 (NO 3 ) was loaded into a platinum crucible, placed in a muffle furnace, heated to 515° C., and kept at this temperature for 70 hours to obtain a mixed melt;

[0095] The mixed melt was slowly cooled to 550°C at a rate of 3°C / h, and then rapidly cooled to room temperature at a rate of 15°C / h to obtain Pb 2 Ba 3 (BO 3 ) 3 (NO 3 ) seed crystal;

[0096] 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 6 rpm by the crystal growth controller, and the seed crystal was pulled at a speed of 12 mm / day. At the same time, the temperature was lowered at a rate of 10 ° C / h. After the crystal growth stopped, the Pb with a size of 8 mm × 6 mm × 4 mm was obtained. 2 Ba 3 (BO 3 )3 (NO 3 ) Nonlinear optical crystals;

[0097] Embodiment 14

[0098] Melt growth of Pb 2 Ba 3 (BO 3 ) 3 (NO 3 ) Nonlinear optical crystals:

[0099] The compound Pb prepared in Example 4 2 Ba 3 (BO 3 ) 3 (NO 3 ) The powder is loaded into a platinum crucible, placed in a muffle furnace, heated to 490° C., and kept at this temperature for 120 hours to obtain a mixed melt;

[0100] The mixed melt was slowly cooled to 440°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 2 Ba 3 (BO 3 ) 3 (NO 3 ) seed crystal;

[0101] 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 0.2°C / h, and the crystal was grown for 60 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 5mm×3mm×2mm. 2 Ba 3 (BO 3 ) 3 (NO 3 )Nonlinear optical crystals.

[0102] Embodiment 15

[0103] Melt growth of Pb 2 Ba 3 (BO 3 ) 3 (NO 3 ) Nonlinear optical crystals:

[0104] The compound Pb prepared in Example 5 2 Ba 3 (BO 3 ) 3 (NO 3) was loaded into a platinum crucible, placed in a muffle furnace, heated to 515° C., and kept at this temperature for 70 hours to obtain a mixed melt;

[0105] The obtained mixed melt was slowly cooled to 460°C at a rate of 0.1°C / h, and then rapidly cooled to room temperature at a rate of 3°C / h to obtain Pb 2 Ba 3 (BO 3 ) 3 (NO 3 ) seed crystal;

[0106] The crystal was grown in the compound melt by the pyrolysis method: the obtained seed crystal was fixed on the seed crystal rod, and the seed crystal was placed from the top of the prepared melt. The temperature was lowered at a rate of 1°C / h, and the crystal was allowed to grow for 20 hours. The crystal was slowly lifted but not separated from the liquid surface to continue growing. This was repeated 3 times. After the crystal growth stopped, a Pb crystal with a size of 7mm×4mm×3mm was obtained. 2 Ba 3 (BO 3 ) 3 (NO 3 )Nonlinear optical crystals.

[0107] Example 16

[0108] Melt growth of Pb 2 Ba 3 (BO 3 ) 3 (NO 3 ) Nonlinear optical crystals:

[0109] The compound Pb prepared in Example 6 2 Ba 3 (BO 3 ) 3 (NO 3 ) was loaded into a platinum crucible, placed in a muffle furnace, heated to 530° C., and kept at this temperature for 40 hours to obtain a mixed melt;

[0110] 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 2 Ba 3 (BO 3 ) 3 (NO 3 ) seed crystal;

[0111] 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°C / h, the crystal was grown for 40 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 11mm×5mm×3mm was obtained. 2 Ba 3 (BO 3 ) 3 (NO 3 ) Nonlinear optical crystals;

[0112] Embodiment 17

[0113] Melt growth of Pb 2 Ba 3 (BO 3 ) 3 (NO 3 ) Nonlinear optical crystals:

[0114] The compound Pb prepared in Example 7 2 Ba 3 (BO 3 ) 3 (NO 3 ) The powder was placed in a platinum crucible, heated to 525° C., and kept at this temperature for 50 hours to obtain a mixed melt;

[0115] The mixed melt was slowly cooled to 470°C at a rate of 1.2°C / h, and then rapidly cooled to room temperature at a rate of 6°C / h to obtain Pb 2 Ba 3 (BO 3 ) 3 (NO 3 ) seed crystal;

[0116] 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 2 Ba 3 (BO 3 ) 3 (NO 3 ) polycrystalline powder is placed in a crucible, and then the platinum crucible is sealed, the temperature of the growth furnace is raised to 530°C, and the temperature is kept constant for 60 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 4 mm / day, and the temperature is reduced to 420°C at a cooling rate of 2°C / h. After the growth is completed, the temperature is quickly reduced to room temperature at a rate of 20°C / h, and a Pb nanoparticle with a size of 7 mm×5 mm×4 mm is obtained. 2 Ba 3 (BO 3 ) 3 (NO 3)Nonlinear optical crystals.

[0117] Embodiment 18

[0118] Melt growth of Pb 2 Ba 3 (BO 3 ) 3 (NO 3 ) Nonlinear optical crystals:

[0119] The compound Pb prepared in Example 4 2 Ba 3 (BO 3 ) 3 (NO 3 ) was loaded into a platinum crucible, placed in a muffle furnace, heated to 525° C., and kept at this temperature for 80 hours to obtain a mixed melt;

[0120] The mixed melt was slowly cooled to 450°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 2 Ba 3 (BO 3 ) 3 (NO 3 ) seed crystal;

[0121] 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 2 Ba 3 (BO 3 ) 3 (NO 3 ) is placed in a crucible, and then the platinum crucible is sealed. The temperature of the growth furnace is raised to 530°C and kept constant for 30 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 mm / day. At the same time, the growth temperature is kept unchanged. After the growth is completed, the crucible is quickly lowered to room temperature at a rate of 5°C / h, and a Pb with a size of 12 mm×7 mm×5 mm is obtained. 2 Ba 3 (BO 3 ) 3 (NO 3 ) Nonlinear optical crystals;

[0122] Embodiment 19

[0123] Melt growth of Pb 2 Ba 3 (BO 3 ) 3 (NO 3 ) Nonlinear optical crystals:

[0124] Compound Pb prepared in Example 9 2Ba 3 (BO 3 ) 3 (NO 3 ) is loaded into a platinum crucible, placed in a muffle furnace, heated to 480° C., and kept at this temperature for 10 hours to obtain a mixed melt;

[0125] The mixed melt was slowly cooled to 380°C at a rate of 4°C / h, and then rapidly cooled to room temperature at a rate of 2.5°C / h to obtain Pb 2 Ba 3 (BO 3 ) 3 (NO 3 ) seed crystal;

[0126] 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 2 Ba 3 (BO 3 ) 3 (NO 3 ) into a crucible, and then the platinum crucible is sealed, the temperature of the growth furnace is raised to 740°C, and the temperature is kept constant for 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 10 mm / day. At the same time, the growth temperature is kept unchanged. After the growth is completed, the crucible is quickly lowered to room temperature at a rate of 15°C / h, and a Pb with a size of 12 mm×7 mm×3 mm is obtained. 2 Ba 3 (BO 3 ) 3 (NO 3 ) Nonlinear optical crystals;

[0127] Embodiment 20

[0128] Growth of Pb by high temperature melt method 2 Ba 3 (BO 3 ) 3 (NO 3 ) Nonlinear optical crystals:

[0129] The compound Pb prepared in Example 6 was added in a molar ratio of 1:0.3. 2 Ba 3 (BO 3 ) 3 (NO 3 ) Polycrystalline powder and flux B 2 O 3 Mix well, put into a platinum crucible, heat to 490°C, and keep the temperature constant for 120 hours to obtain a mixed melt;

[0130] Preparation of seed crystal: The obtained mixed melt was placed in a single crystal furnace, slowly cooled to 420°C at a rate of 0.2°C / h, and then rapidly cooled to room temperature at a rate of 8°C / h to obtain Pb 2 Ba 3 (BO 3 ) 3 (NO 3 ) seed crystal;

[0131] 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 2 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 6 mm × 4 mm × 3 mm was obtained. 2 Ba 3 (BO 3 ) 3 (NO 3 )Nonlinear optical crystals.

[0132] Embodiment 21

[0133] Growth of Pb by high temperature melt method 2 Ba 3 (BO 3 ) 3 (NO 3 ) Nonlinear optical crystals:

[0134] The compound Pb obtained in Example 4 was added in a molar ratio of 1:2 2 Ba 3 (BO 3 ) 3 (NO 3 ) and flux H 3 BO 3 Mix well, put into a platinum crucible, heat to 470°C, and keep the temperature constant for 20 hours to obtain a mixed melt;

[0135] Preparation of seed crystal: The obtained mixed melt was placed in a single crystal furnace, slowly cooled to 420°C at a rate of 1°C / h, and then rapidly cooled to room temperature at a rate of 12°C / h to obtain Pb 2 Ba 3 (BO 3 ) 3 (NO 3 ) seed crystal;

[0136] 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 5 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 9 mm × 4 mm × 3 mm was obtained. 2 Ba 3 (BO3 ) 3 (NO 3 )Nonlinear optical crystals.

[0137] Embodiment 22

[0138] Growth of Pb by high temperature melt method 2 Ba 3 (BO 3 ) 3 (NO 3 ) Nonlinear optical crystals:

[0139] The compound Pb obtained in Example 8 was added in a molar ratio of 1:0.5 2 Ba 3 (BO 3 ) 3 (NO 3 ) is mixed evenly with flux PbO, then put into a platinum crucible, heated to 475°C, and kept at this temperature for 70 hours to obtain a mixed melt;

[0140] Preparation of seed crystal: The obtained mixed melt was placed in a single crystal furnace, slowly cooled to 430°C at a rate of 1.5°C / h, and then rapidly cooled to room temperature at a rate of 6°C / h to obtain Pb 2 Ba 3 (BO 3 ) 3 (NO 3 ) seed crystal;

[0141] 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 0.8 °C / h. After the crystal growth stopped, a Pb crystal with a size of 6 mm × 2 mm × 2 mm was obtained. 2 Ba 3 (BO 3 ) 3 (NO 3 )Nonlinear optical crystals.

[0142] Embodiment 23

[0143] Growth of Pb by high temperature melt method 2 Ba 3 (BO 3 ) 3 (NO 3 ) Nonlinear optical crystals:

[0144] The compound Pb obtained in Example 7 was added in a molar ratio of 1:2.5. 2 Ba 3 (BO 3 ) 3 (NO3 ) and flux PbF 2 Mix well, put into a platinum crucible, heat to 500°C, keep constant temperature for 100 hours, and obtain a mixed melt;

[0145] Preparation of seed crystal: The obtained mixed melt was placed in a single crystal furnace, slowly cooled to 450°C at a rate of 1.5°C / h, and then rapidly cooled to room temperature at a rate of 7°C / h to obtain Pb 2 Ba 3 (BO 3 ) 3 (NO 3 ) seed crystal;

[0146] 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 12 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 × 3 mm was obtained. 2 Ba 3 (BO 3 ) 3 (NO 3 )Nonlinear optical crystals.

[0147] Embodiment 24

[0148] Growth of Pb by vacuum encapsulation 2 Ba 3 (BO 3 ) 3 (NO 3 ) Nonlinear optical crystals:

[0149] The compound Pb prepared in Example 8 was added in a molar ratio of 1:0.2. 2 Ba 3 (BO 3 ) 3 (NO 3 ) and flux H 3 BO 3 Mix well, put into a Φ40mm quartz tube, and evacuate the quartz tube to a vacuum degree of 1×10 -3 Pa, sealed at high temperature, placed in a muffle furnace, heated to 485 ° C, kept at this temperature for 40 hours, then cooled to 350 ° C at a rate of 1.5 ° C / h, and then quickly cooled to room temperature at a rate of 9 ° C / h, thus obtaining a Pb with a size of 5 mm × 2 mm × 1 mm. 2 Ba 3 (BO 3 ) 3 (NO 3 )Nonlinear optical crystals.

[0150] Embodiment 25

[0151] Growth of Pb by vacuum encapsulation 2 Ba 3 (BO 3 ) 3 (NO 3 ) Nonlinear optical crystals:

[0152] The compound Pb2Ba3(BO3)3(NO3) obtained in Example 9 was mixed with flux B in a molar ratio of 1:0.5. 2 O 3 Mix well, put into a Φ40mm quartz tube, and evacuate the quartz tube 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. 2 Ba 3 (BO 3 ) 3 (NO 3 )Nonlinear optical crystals.

[0153] Embodiment 26

[0154] Growth of Pb by vacuum encapsulation 2 Ba 3 (BO 3 ) 3 (NO 3 ) Nonlinear optical crystals:

[0155] The compound Pb obtained in Example 10 was added in a molar ratio of 1:1. 2 Ba 3 (BO 3 ) 3 (NO 3 ) and flux PbO were mixed evenly, loaded into a Φ40 mm 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 495°C, kept constant for 80 hours, then cooled to 455°C at a rate of 2°C / h, and then quickly cooled to room temperature at a rate of 6°C / h to obtain a Pb with a size of 6mm×3mm×1mm. 2 Ba 3 (BO 3 ) 3 (NO 3 )Nonlinear optical crystals.

[0156] Embodiment 27

[0157] Any Pb obtained in Examples 11-262 Ba 3 (BO 3 ) 3 (NO 3 ) 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 2 Ba 3 (BO 3 ) 3 (NO 3 ) single crystal 3, produces green frequency-doubled 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, nitrogen and oxygen, characterized in that The chemical formula of this compound is Pb2Ba3(BO3)3(NO3), the molecular weight is 1039.98, it belongs to the orthorhombic system, and the space group is C 2221, the unit cell parameters are a =10.4818(5) Å, b =14.4102(7) Å, c =8.0332(4) Å, α= 90°, β= 90°, γ= 90°, unit cell volume is 1213.37(10) Å 3 , made by solid phase method or vacuum packaging method.

2. A method for preparing the compound lead barium boron nitrogen oxygen 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 nitrogen oxide compound: The Pb-containing compound, the Ba-containing compound, the B-containing compound and the N-containing compound are uniformly mixed in a molar ratio of Pb:Ba:B:N=2:3:3:1, loaded into a platinum crucible, placed in a muffle furnace, heated to 500-600°C, and kept at a constant temperature for 60-120 hours to obtain the compound Pb2Ba3(BO3)3(NO3), 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 N-containing compound is Pb(NO3)2 and Ba(NO3)2; The vacuum packaging method is used to prepare the lead barium boron nitrogen oxygen compound: The Pb-containing compound, the Ba-containing compound, the B-containing compound and the N-containing compound are mixed evenly in a molar ratio of Pb:Ba:B:N=2:3:3:1, and the mixture is placed in a quartz tube. The quartz tube is evacuated to a vacuum degree of 1×10 −3 Pa, high temperature sealed and placed in a muffle furnace, heated to 450-550°C at a rate of 5-10°C / h, and kept at this temperature for 60-120 hours to obtain the compound Pb2Ba3(BO3)3(NO3), 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 N-containing compound is Pb(NO3)2 and Ba(NO3)2.

3. A lead-barium-boron-nitrogen-oxygen nonlinear optical crystal, characterized in that The chemical formula of the crystal is Pb2Ba3(BO3)3(NO3), the molecular weight is 1039.98, it belongs to the orthorhombic system, and the space group is C 2221, the unit cell parameters are a =10.4818(5) Å, b =14.4102(7) Å, c =8.0332(4) Å, α= 90°, β= 90°, γ= 90°, unit cell volume is 1213.37(10) Å 3 .

4. A method for preparing a lead-barium-boron-nitrogen-oxygen 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-nitrogen-oxygen nonlinear optical crystals is specifically performed in the following steps: a. Pb-containing compound, Ba-containing compound, B-containing compound and N-containing compound are mixed uniformly in a molar ratio of Pb:Ba:B:N=2:3:3:1, and the mixture is put into a platinum crucible, placed in a muffle furnace, heated to 500-600°C, and kept at this temperature for 48-120 hours to obtain compound Pb2Ba3(BO3)3(NO3), 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; and the N-containing compound is Pb(NO3)2 and Ba(NO3)2; b. The compound Pb2Ba3(BO3)3(NO3) prepared in step a is placed in a platinum crucible, placed in a muffle furnace, heated to 500-600°C, and kept at this temperature for 10-60 hours to obtain a mixed melt; c. Slowly cool the mixed melt obtained in step b to 450° C. at a rate of 0.1-4° C. / h, and then quickly cool it to room temperature at a rate of 5-10° C. / h to obtain Pb2Ba3(BO3)3(NO3) seed crystals; d. Growing crystals in the compound melt by the pulling 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 2-15 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 0.1-5°C / h. After the crystal growth stops, the Pb2Ba3(BO3)3(NO3) nonlinear optical crystal is obtained; 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, place the seed crystal from the top of the melt obtained in step b, cool it down at a rate of 0.1-3°C / 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 after the crystal growth stops, a Pb2Ba3(BO3)3(NO3) nonlinear optical crystal is obtained; Or use the crucible lowering method to grow crystals in the compound melt: place the seed crystal prepared in step c at the bottom of the crucible, then place the compound Pb2Ba3(BO3)3(NO3) prepared in step a into the crucible, then seal the platinum crucible, raise the growth furnace temperature to 480-520°C, keep the temperature constant for 48-240 hours, adjust the crucible position to make the seed crystal slightly melt, then lower the crucible at a rate of 1-10 mm / day, and at the same time, keep the growth temperature unchanged, or lower it to 450°C at a cooling rate of 2°C / h. After the growth is completed, quickly lower it to room temperature at a rate of 5-15°C / h to obtain a Pb2Ba3(BO3)3(NO3) nonlinear optical crystal; The high temperature melt method for growing lead barium boron nitrogen oxygen nonlinear optical crystals is specifically performed in the following steps: a. Pb:Ba:B:N=2:3:3:1 in molar ratio. Evenly mix the Pb-containing compound, the Ba-containing compound, the B-containing compound and the N-containing compound, put them into a platinum crucible, place them in a muffle furnace and heat them to 490-530°C, and keep the temperature constant for 48-240 hours to obtain a polycrystalline powder of the compound Pb2Ba3(BO3)3(NO3), 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 N-containing compound is Pb(NO3)2 and Ba(NO3)2; b. Mix the compound Pb2Ba3(BO3)3(NO3) obtained in step a with a flux in a molar ratio of 1:0.1-3, put into a platinum crucible, heat to 450-550°C, and keep the temperature constant for 10-150 hours to obtain a mixed melt; the flux is H3BO3, B2O3 or PbO; c. Preparation of seed crystals: placing the mixed melt obtained in step b in a single crystal furnace, slowly cooling the temperature to 600°C at a rate of 0.1-3°C / h, and then rapidly cooling the temperature to room temperature at a rate of 5-10°C / h to obtain Pb2Ba3(BO3)3(NO3) seed crystals; d. Growing crystals: Fix the seed crystals obtained in step c on the seed crystal rod, place the seed crystals from above the mixed melt obtained in step b, apply a crystal rotation of 3-10 rpm through a crystal growth controller, cool at a rate of 0.1-3°C / h, and after the crystal growth stops, a Pb2Ba3(BO3)3(NO3) nonlinear optical crystal is obtained; The vacuum packaging method for growing lead-barium-boron-nitrogen-oxygen nonlinear optical crystals is specifically performed in the following steps: a. Pb:Ba:B:N=2:3:3:1 in molar ratio. Mix the Pb-containing compound, Ba-containing compound, B-containing compound and N-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 and placed in a muffle furnace, heated to 450-550°C at a rate of 5-10°C / h, and kept at a constant temperature for 60-100 hours to obtain the compound Pb2Ba3(BO3)3(NO3), 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 N-containing compound is Pb(NO3)2 and Ba(NO3)2; b. Mix the compound Pb2Ba3(BO3)3(NO3) obtained in step a with flux in a molar ratio of 1:0.1-3, 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 450-480°C, kept constant for 60-120 hours, then cooled to 400°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 Pb2Ba3(BO3)3(NO3) nonlinear optical crystal, wherein the flux is H3BO3, B2O3 or PbO.

5. A use of the lead-barium-boron-nitrogen-oxygen nonlinear optical crystal as described in claim 3 in preparing the 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 nitrogen oxide 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-nitrogen-oxygen 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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