Barium lanthanum bromoborate compound and barium lanthanum bromoborate nonlinear optical crystal, preparation method and use thereof

Abstract

The present application relates to a kind of compound barium lanthanum bromoborate and a kind of preparation method and purposes of barium lanthanum bromoborate nonlinear optical crystal, the chemical formula of the compound barium lanthanum bromoborate and its nonlinear optical crystal are all Ba 13 Br, the crystal belongs to hexagonal system, and space group is all P 63 mc , cell parameter is a=10.9580 (9) Å, b=10.7828 (6) Å, c=7.0412 (6) Å, V=732.22 (14) Å 3 , molecular weight is 1287.93, and the powder frequency doubling effect is about 6 times KDP (KH2PO4). Compound barium lanthanum bromoborate is synthesized using solid phase reaction method, barium lanthanum bromoborate nonlinear optical crystal is grown using high-temperature melt method or crystal is grown using pulling method, the crystal preparation method is simple, low in cost, and the crystal prepared has large mechanical hardness, and barium lanthanum bromoborate crystal obtained by the method is applied as nonlinear optical frequency doubling device.

Description

Technical Field

[0001] This invention relates to the chemical formula Ba3La4B3O 13 The compound Br, barium lanthanum bromoborate, and its nonlinear optical crystal, the crystal preparation method, and the nonlinear optical device made using the crystal. Background Technology

[0002] Nonlinear optical crystals are important optoelectronic functional materials and a crucial material foundation for optoelectronic technology, particularly laser technology. Nonlinear optical crystal materials can be used to convert laser frequencies and extend laser wavelengths, adjust laser intensity and phase, and achieve holographic storage of laser signals. Therefore, nonlinear optical crystals are indispensable key materials in high-tech and modern military technologies. Countries worldwide prioritize information technology development and incorporate it into their high-tech development plans as a highly valued and supported strategic initiative.

[0003] The requirements for second-order nonlinear optical crystals mainly include a non-centrosymmetric structure, appropriate birefringence, a wide transmission range in the ultraviolet region, a high laser damage threshold, and excellent physicochemical properties. Borate crystals have significant application value in semiconductor lithography, laser micromachining, and photochemical synthesis, and their performance has attracted widespread attention. Due to their large band gap, high laser damage threshold, and stable physicochemical properties, they are ideal for obtaining strong nonlinear optical effects, making them an ideal choice for novel ultraviolet nonlinear optical crystals. Furthermore, the introduction of alkaline earth metal cations and rare earth elements (Ba, La) into borates eliminates dd and ff electronic transitions, making them ideal for ultraviolet transmission. Introducing highly electronegative halide ions (Br₂, Br₂) further enhances their appeal. - It can broaden the transmittance range, shifting the blue cutoff edge to the ultraviolet or even deep ultraviolet region, such as KBe2BO3F2 (KBBF). Therefore, Br-containing... - The synthesis of alkaline earth metal rare earth borates will be an effective means of designing high frequency doubling effects for use in ultraviolet and deep ultraviolet nonlinear optical materials. Summary of the Invention

[0004] The purpose of this invention is to provide a compound, lanthanum barium bromoborate, and a nonlinear optical crystal of lanthanum barium bromoborate, both with the chemical formula Ba3La4B3O. 13 Br.

[0005] Another objective of this invention is to provide a method for synthesizing the compound barium lanthanum bromoborate by solid-state reaction and for growing barium lanthanum bromoborate nonlinear optical crystals by high-temperature melt method or Czochralski method.

[0006] Another object of the present invention is to provide the use of barium lanthanum bromide borate nonlinear optical devices for the fabrication of frequency multipliers, up or down frequency converters, or optical parametric oscillators.

[0007] The technical solution of the present invention is as follows:

[0008] The barium lanthanum bromoborate compound provided by this invention has the chemical formula Ba3La4B3O 13 Br, which is prepared as a barium lanthanum bromoborate compound by a solid-state reaction method according to the following chemical reaction formula:

[0009] 1)5BaCO3+6H3BO3+1BaBr2+4La2O3→2Ba3La4B3O 13 Br + 5CO2↑ + 9H2O↑

[0010] 2)3BaCO3+3H3BO3+2La2O3+1NH4Br→Ba3La4B3O 13 Br + 1NH3↑ + 3CO2↑ + 5H2O↑

[0011] 3)5Ba(OH)2+1BaBr2+6H3BO3+4La2O3→2Ba3La4B3O 13 Br + 14H₂O↑

[0012] 4)3BaO+3H3BO3+2La2O3+1NH4Br→Ba3La4B3O 13 Br + 5H₂O↑ + NH₃↑

[0013] 5)3Ba(OH)2+1NH4Br+3H3BO3+2La2O3→Ba3La4B3O 13 Br + 8H₂O↑ + 1NH₃↑

[0014] 6)5BaO+6H3BO3+4La2O3+1BaBr2→2Ba3La4B3O 13 Br + 9H₂O↑

[0015] 7)5BaCO3+6H3BO3+1BaBr2+8La(NO3)3·6H2O→2Ba3La4B3O 13 Br+24

[0016] NO₂↑ + 57H₂O↑ + 5CO₂↑ + 6O₂↑

[0017] 8)3BaCO3+3H3BO3+4La(NO3)3·6H2O+1NH4Br→Ba3La4B3O 13 Br+1NH3↑+3CO2↑+12NO2↑+29H2O↑+3O2↑

[0018] 9)1Ba(OH)2+2BaCO3+1NH4Br+2La2O3+3H3BO3→Ba3La4B3O 13 Br+1NH3↑+6H2O↑+2CO2↑

[0019] 10)2Ba(OH)2+1BaCO3+1NH4Br+2La2O3+3H3BO3→Ba3La4B3O 13 Br+1NH3↑+7H2O↑+1CO2↑

[0020] 11) 1Ba(OH)2 + 2BaCO3 + 1NH4Br + 4La(NO3)3·6H2O + 3H3BO3 → Ba3La4B3O 13 Br+1NH3↑+30H2O↑+2CO2↑+15O2↑

[0021] 12) 2Ba(OH)2 + 1BaCO3 + 1NH4Br + 4La(NO3)3·6H2O + 3H3BO3 → Ba3La4B3O 13 Br+1NH3↑+31H2O↑+1CO2↑+15O2↑

[0022] 13)10BaSO4+12H3BO3+2BaBr2+8La2O3→4Ba3La4B3O 13 Br+10SO2↑+18H2O↑+5O2↑

[0023] 14) 6BaSO4 + 6H3BO3 + 4La2O3 + 2NH4Br → 2Ba3La4B3O 13 Br+2NH3↑+6SO2↑+10H2O↑+3O2↑

[0024] 15) 5BaNO3 + 6H3BO3 + 1BaBr2 + 4La2O3 → 2Ba3La4B3O 13 Br+5CO2↑+9H2O↑

[0025] 16) 3BaNO3 + 3H3BO3 + 2La2O3 + 1NH4Br → Ba3La4B3O 13 Br+1NH3↑+3NO2↑+5H2O↑

[0026] 17)1Ba(OH)2+2BaNO3+1NH4Br+2La2O3+3H3BO3→Ba3La4B3O 13 Br+1NH3↑+6H2O↑+2NO2↑

[0027] 18)2Ba(OH)2+1BaNO3+1NH4Br+2La2O3+3H3BO3→Ba3La4B3O 13 Br + 1NH3↑ + 7H2O↑ + 1NO2↑

[0028] This invention provides a nonlinear optical crystal of barium lanthanum bromoborate, characterized in that the chemical formula of the crystal is Ba3La4B3O. 13 Br, with a molecular weight of 1287.93, lacks a center of symmetry, belongs to the hexagonal crystal system, and has the space group P63(mc). The compound is Ba3La4B3O. 13 The unit cell parameters of Br are Its powder frequency doubling effect is approximately 6 times that of KDP (KH2PO4).

[0029] A method for preparing a nonlinear optical crystal of barium lanthanum bromoborate, characterized by growing the crystal using a high-temperature melt method or a Czochralski method, with the specific operations as follows:

[0030] a. Mix the barium lanthanum bromoborate compound single-phase polycrystalline powder with a flux, heat it to 650-1000℃ at a heating rate of 1-30℃ / h, hold it at the temperature for 5-80 hours to obtain a mixed melt, and then cool it down to 500-800℃. The molar ratio of the barium lanthanum bromoborate compound single-phase polycrystalline powder to the flux is 1:0.5-25.

[0031] Alternatively, a mixture of barium-containing compounds, lanthanum-containing compounds, boron-containing compounds, and bromine-containing compounds, or a mixture of barium-containing compounds, lanthanum-containing compounds, boron-containing compounds, and bromine-containing compounds with a flux, can be heated to 650-1000℃ at a heating rate of 1-30℃ / h, held at that temperature for 5-80 hours to obtain a mixed melt, and then cooled to 500-800℃. The molar ratio of barium-containing compounds, lanthanum-containing compounds, boron-containing compounds, and bromine-containing compounds to flux is 2.5-3.3:3.5-4.2:2.5-0.7-1.3:0.1-30.

[0032] The fluxes mainly include single fluxes such as BaCO3, BaBr2, BaO, H3BO3, PbO, NaBr, Na2CO3, LiBr, Li2CO3, KBr, K2CO3, LiBO2, etc., and other composite fluxes such as BaCO3-BaBr2, BaCO3-BaO, BaCO3-H3BO3, BaCO3-NaBr, BaCO3-KBr, BaCO3-PbO, BaCO3-LiBr, BaBr2-BaO, BaBr2-PbO, BaBr2-NaBr, BaBr2-Na2CO3, BaBr2-LiBr, BaBr2-KBr, BaBr2-K2CO3, BaO-H3BO3, BaO-PbO, BaO-NaBr, BaO-Na2CO3, BaO-LiBr, BaO-Li2CO3, BaO-KBr, BaO-K2CO3, BaO-LiBO2, H3BO3-PbO, H3BO3-Na2CO3, H3BO3-Li2CO3, H3BO3-KBr, H3BO3-K2CO3, H3BO3-LiBO2, BaCO3-NaBr-H3BO3, BaCO3-BaO-H3BO3, BaCO3-LiBr-H3BO3, BaCO3-KBr-H3BO3, BaBr2-BaO-H3BO3, BaBr2-NaBr-H3BO3, BaBr2-LiBr-H3BO3, BaO-BaBr2-H3BO3, BaO-NaBr-H3BO3, H3BO3-PbO-BaBr2, NaBr-PbO-H3BO3, KBr-PbO-H3BO3, Li2CO3-PbO-H3BO3, LiBO2-PbO-H3BO3, H3BO3-KBr-NaBr, H3BO3-K2CO3-Na2CO3, H3BO3-K2CO3-NaBr, H3BO3-KBr-Na2CO3, H3BO3-KBr-Na2CO3-BaBr2, H3BO3-K2CO3-NaBr-BaBr2, H3BO3-PbO-NaBr-BaBr2, HBO3-LiBr-NaBr-BaBr2, H3BO3-K2CO3-LiBr-BaBr2, etc.

[0033] A method for preparing a nonlinear optical crystal of barium lanthanum bromoborate, characterized by using a solid-state synthesis method with the single-phase polycrystalline powder of barium lanthanum bromoborate, comprising the following steps: mixing a barium-containing compound, a lanthanum-containing compound, a boron-containing compound, and a bromine-containing compound and preparing the compound by a solid-state reaction method, wherein the molar ratio of barium in the barium-containing compound, lanthanum in the lanthanum-containing compound, boron in the boron-containing compound, and bromine in the bromine-containing compound is 2.5-3.3:3.5-4.2:2.5-0.7-1.3; uniformly mixing the barium-containing compound, lanthanum-containing compound, boron-containing compound, and bromine-containing compound raw materials, grinding them, and placing them in a muffle furnace for pre-calcination to remove moisture and gases from the raw materials, cooling to room temperature, removing them, grinding them again, and then calcining them in a muffle furnace, heating to 600-1000℃, holding at that temperature for 72 hours, cooling to room temperature, and removing the ground single-phase polycrystalline powder of barium lanthanum bromoborate.

[0034] b. Preparation of barium lanthanum broborate seed crystals: The mixed melt obtained in step a is slowly cooled to room temperature at a rate of 3-10℃ / h to spontaneously crystallize and obtain barium lanthanum broborate seed crystals.

[0035] c. Place the crucible containing the mixed melt obtained in step a into the crystal growth furnace, fix the seed crystal obtained in step b on the seed crystal rod, lower the seed crystal from the top of the crystal growth furnace, preheat the seed crystal for 5-60 minutes, lower the seed crystal to the surface of the mixed melt or the mixed melt for remelting, keep the temperature constant for 5-60 minutes, and reduce the temperature to the saturation temperature at a rate of 1-60℃ / h.

[0036] d. Then, slowly cool down at a rate of 0.1-5℃ / day, and grow the crystal by rotating the seed crystal rod at a speed of 0-60 rpm. After the single crystal grows to the required size, lift the crystal off the surface of the mixed melt and cool it down to room temperature at a rate of 1-80℃ / h. Then take the crystal out of the furnace to obtain the barium lanthanum bromoborate nonlinear optical crystal.

[0037] The fluxing agents described above have the following molar ratios: BaCO3-BaBr2 system: BaCO3 to BaBr2 = 1-3:2-5; BaCO3-BaO system: BaCO3 to BaO = 1-3:3-6; BaCO3-H3BO3 system: BaCO3 to H3BO3 = 1-5:3-7; BaCO3-NaBr system: BaCO3 to NaBr = 1-5:2-8; BaCO3-KBr system: BaCO3 to KBr = 1-8:2-5; BaCO3-PbO system: BaCO3 to PbO = 1. -10:3-6; In the BaCO3-LiBr system, the molar ratio of BaCO3 to LiBr is 1-7:1-6; In the BaBr2-PbO system, the molar ratio of BaBr2 to PbO is 1-7:1-6; In the BaBr2-NaBr system, the molar ratio of BaBr2 to NaBr is 1-8:2-5; In the BaBr2-Na2CO3 system, the molar ratio of BaBr2 to Na2CO3 is 1-10:3-6; In the BaBr2-LiBr system, the molar ratio of BaBr2 to LiBr is 1-7:5-6; In the H3BO3-PbO system, the molar ratio of H3BO3 to PbO is... The molar ratios of H3BO3 and Na2CO3 in the H3BO3-Na2CO3 system are 1-7:2-6; 1-6:1-5 in the H3BO3-Li2CO3 system; 1-6:2-6 in the H3BO3-KBr system; 1-6:4-6 in the H3BO3-K2CO3 system; 1-6:2-6 in the H3BO3-LiBO2 system; and 1-5:4-6 in the H3BO3-LiBO2 system. The molar ratios of H3BO3 and LiBO2 in the BaO-Na2CO3 system are also mentioned. The molar ratio of BaO to Na2CO3 is 1:4:2:6; in the BaO-KBr system, the molar ratio of Na2CO3 to Na2CO3 is 1:6:1:5; in the BaCO3-NaBr-H3BO3 system, the molar ratio of BaCO3, NaBr, and H3BO3 is 1:5:2:6:3:8; in the BaCO3-BaO-H3BO3 system, the molar ratio of BaCO3, BaO, and H3BO3 is 0.5:1:6:3:8; and in the BaCO3-LiBr-H3BO3 system, the molar ratio of BaCO3, LiBr, and H3BO3 is 1:5:0.5:6:2.9-8; In the BaBr2-LiBr-H3BO3 system, the molar ratio of BaBr2, LiBr, and H3BO3 is 1-6:1-7:3-8; In the BaO-BaBr2-H3BO3 system, the molar ratio of BaO, BaBr2, and H3BO3 is 1-3:1-4:3-10; In the BaO-NaBr-H3BO3 system, the molar ratio of BaO, NaBr, and H3BO3 is 1-5:1-9:3-12; In the H3BO3-PbO-BaBr2 system, the molar ratio of H3BO3, PbO, and BaBr2 is 2-5:1-6:3-8; In the NaBr-PbO-H3BO3 system... In the O3 system, the molar ratio of NaBr, PbO, and H3BO3 is 2.9:1.7:1.10; in the KBr-PbO-H3BO3 system, the molar ratio of KBr, PbO, and H3BO3 is 2.5:1.6:2.8; in the Li2CO3-PbO-H3BO3 system, the molar ratio of Li2CO3, PbO, and H3BO3 is 2.5:1.10:2.11; in the LiBO2-PbO-H3BO3 system, the molar ratio of LiBO2, PbO, and H3BO3 is 0.5:1.5:10:2.10; in the H3BO3-KBr-NaBr system, the molar ratio of H3BO3, KBr, and PbO is 2.5:1.7:1.10; in the H3BO3-KBr-NaBr system, the molar ratio of H3BO3, KBr, and PbO is 0.5:1.5:10:2.10. The molar ratio of H3BO3, KBr, Na2CO3 to BaBr2 in the H3BO3-KBr-Na2CO3-BaBr2 system is 2-5:1-10:2-9; the molar ratio of H3BO3, KBr, Na2CO3 to BaBr2 in the H3BO3-KBr-NaBr-BaBr2 system is 1-21:1-10:2-8:1-8; the molar ratio of H3BO3, K2CO3, NaBr to BaBr2 in the H3BO3-PbO-NaBr-BaBr2 system is 1-20: In the H3BO3-LiBr-NaBr-BaBr2 system, the molar ratio of H3BO3, K2CO3, NaBr, and BaBr2 is 1-10:2-8:1-8; in the H3BO3-K2CO3-LiBr-BaBr2 system, the molar ratio is 1-21:2-10:2-9:1-7; and in the H3BO3-KBr-NaBr-BaBr2 system, the molar ratio is 1-18:1-9:2-10:1-9.

[0038] The present invention provides a barium lanthanum bromoborate nonlinear optical crystal, characterized in that the chemical formula of the crystal is Ba3La4B3O. 13 Br, with a molecular weight of 1287.93, lacks a center of symmetry, belongs to the hexagonal crystal system, and has space group P63(mc). Its compound is Ba3La4B3O.13 The unit cell parameters of Br are Its powder frequency doubling effect is approximately 5 times that of KDP (KH2PO4).

[0039] During the growth of barium lanthanum bromoborate nonlinear optical crystals, self-fluxing fluxes such as BaCO3, BaBr2, Ba(OH)2, BaO, H3BO3, and B2O3 are used, along with other fluxes such as NaBr, LiBr, KBr, Na2CO3, Li2CO3, and K2CO3, as well as fluxes such as BaBr2-Ba(OH)2, BaBr2-BaO, BaBr2-H3BO3, BaBr2-B2O3, Ba(OH)2-BaO, Ba(OH)2-H3BO3, Ba(OH)2-B2O3, BaO-H3BO3, BaCO3-BaBr2, BaCO3-BaO, and BaCO3-H3B O3, BaCO3-NaBr, BaCO3-KBr, BaCO3-PbO, BaCO3-LiBr, BaBr2-BaO, BaBr2-PbO, BaBr2-NaBr, BaBr2-Na2CO3, BaBr2-LiBr, BaBr2-KBr, BaBr2-K2C O3, BaO-H3BO3, BaO-PbO, BaO-NaBr, BaO-Na2CO3, BaO-LiBr, BaO-Li2CO3, BaO-KBr, BaO-K2CO3, BaO-LiBO2, H3BO3-PbO, H3BO3-Na2CO3, H3BO3-L i2CO3, H3BO3-KBr, H3BO3-K2CO3, H3BO3-LiBO2, BaCO3-NaBr-H3BO3, BaCO3-BaO-H3BO3, BaCO3-LiBr-H3BO3, BaCO3-KBr-H3BO3, BaBr2-BaO-H3B O3, BaBr2-NaBr-H3BO3, BaBr2-LiBr-H3BO3, BaO-BaBr2-H3BO3, BaO-NaBr-H3BO3, H3BO3-PbO-BaBr2, NaBr-PbO-H3BO3, KBr-PbO-H3BO3, Li2CO3 -PbO-H3BO3, LiBO2-PbO-H3BO3, H3BO3-KBr-NaBr, H3BO3-K2CO3-Na2CO3, H3BO3-K2CO3-NaBr, H3BO3-KBr-Na2CO3, H3BO3-KBr-Na2CO3-BaBr2, H3BO3-K2CO3-NaBr-BaBr2, H3BO3-PbO-NaBr-BaBr2, H3BO3-LiBr-NaBr-BaBr2 or other composite fluxes, the products have high purity, easy crystal growth and are transparent without encapsulation, with advantages such as fast growth rate, low cost and easy to obtain large-sized crystals;The barium lanthanum bromoborate nonlinear optical crystal described herein is used to fabricate frequency doubling generators, up-frequency converters, down-frequency converters, or optical parametric oscillators. The obtained crystal possesses advantages such as a relatively wide transmission band, high hardness, good mechanical properties, resistance to breakage and deliquescence, and ease of processing and storage. Nonlinear optical devices fabricated using the barium lanthanum bromoborate nonlinear optical crystal obtained by the method described in this invention, at room temperature, using an Nd:YAG Q-switched laser as the light source, with an incident infrared wavelength of 1064 nm, output green laser light with a wavelength of 532 nm, and the laser intensity is equivalent to 6 times that of KDP (KH₂PO₄). Attached Figure Description

[0040] Figure 1 The present invention is Ba3La4B3O 13 X-ray diffraction pattern of Br powder.

[0041] Figure 2 The present invention is Ba3La4B3O 13 A schematic diagram illustrating the working principle of a nonlinear optical device fabricated from Br crystal, where 1 represents the laser, 2 represents the emitted beam, and 3 represents Ba3La4B3O. 13 Br crystal, 4 is the emitted beam, and 5 is the filter. Detailed Implementation

[0042] The present invention will now be described in detail with reference to the accompanying drawings and embodiments:

[0043] Example 1:

[0044] According to the reaction formula: 5BaCO3 + 6H3BO3 + 2BaBr2 + 4La2O3 → 2Ba3La4B3O 13 Br + 2CO2↑ + 9H2O↑ synthesize Ba3La4B3O 13 Br compounds:

[0045] BaCO3, H3BO3, BaBr2, and La2O3 were weighed out in a molar ratio of 5:6:2:4 and placed in a mortar. The mixture was then carefully ground and placed into an open corundum crucible (Φ100mm×100mm). The crucible was placed in a muffle furnace and slowly heated to 300℃, held at that temperature for 24 hours, and then cooled to room temperature. After a second grinding, the mixture was placed back into the muffle furnace and heated to 950℃, held at that temperature for 24 hours, and then cooled to room temperature. After a third grinding, the mixture was placed back into the muffle furnace and held at 950℃ for 48 hours. The resulting single-phase polycrystalline powder of barium lanthanum bromoborate was obtained. X-ray analysis of the product was performed. The obtained X-ray spectrum was similar to that of barium lanthanum bromoborate (Ba3La4B3O3). 13 The X-ray spectra obtained from the Br single crystal structure are consistent;

[0046] The obtained barium lanthanum bromoborate Ba3La4B3O 13 Br compound single-phase polycrystalline powder and flux H3BO3-KBr-NaBr in molar ratio Ba3La4B3O 13 The mixture of Br:H3BO3-KBr-NaBr = 1:3, where the molar ratio of H3BO3, KBr and NaBr is 6:3:5, is placed in an open platinum crucible with a diameter of 80mm × 80mm and heated to 900℃ at a heating rate of 30℃ / h. The temperature is held for 15 hours to obtain a mixed melt, which is then cooled to 880℃.

[0047] The temperature was slowly reduced to room temperature at a rate of 0.5℃ / h, and barium lanthanum bromoborate seed crystals were obtained by spontaneous crystallization.

[0048] Crystal growth in compound melt: The obtained Ba3La4B3O 13 The Br seed crystal is fixed on the seed crystal rod and dropped from the top of the crystal growth furnace. The seed crystal is preheated on the surface of the mixed melt for 10 minutes, then immersed in the melt to allow the seed crystal to remelt in the mixed melt. The temperature is kept constant for 30 minutes and then rapidly cooled to the saturation temperature of 865℃.

[0049] The temperature is then lowered at a rate of 2℃ / day, and the seed crystal rod is rotated at a speed of 10 rpm. After crystal growth is complete, the crystal is removed from the liquid surface and cooled to room temperature at a rate of 10℃ / hour. This yields a Ba3La4B3O crystal with dimensions of 56mm×40mm×30mm. 13 Br crystal.

[0050] In the reaction formula, barium carbonate can be replaced by other barium salts such as barium bromide, barium nitrate, barium oxalate, or barium sulfate, or by barium oxide or barium hydroxide. Lanthanum oxide can be replaced by other lanthanum salts such as lanthanum carbonate, lanthanum nitrate, lanthanum bromide, lanthanum oxalate, or lanthanum sulfate, or by lanthanum hydroxide. Boric acid can be replaced by boron oxide.

[0051] Example 2:

[0052] According to the reaction formula: 3BaCO3 + 3H3BO3 + 2La2O3 + 1NH4Br → Ba3La4B3O 13 Br + NH3↑ + 4NO2↑ + 3CO2↑ + 5H2O↑ synthesize Ba3La4B3O 13 Br compounds:

[0053] BaCO3, H3BO3, La2O3, and NH4Br were weighed directly in a molar ratio of 3:3:2:1. The weighed raw materials were mixed with flux H3BO3-PbO in a molar ratio of 1:4, wherein the molar ratio of H3BO3 to PbO was 3:5. The mixture was placed in an open platinum crucible with a diameter of 80mm and a diameter of 80mm, heated to 870℃, and held at that temperature for 60 hours to obtain a mixed melt. The melt was then cooled to 850℃.

[0054] The temperature was slowly lowered to room temperature at a rate of 1.5℃ / h to spontaneously crystallize and obtain barium lanthanum bromoborate seed crystals.

[0055] Ba3La4B3O will be obtained 13 The Br seed crystal is fixed on the seed crystal rod and dropped from the top of the crystal growth furnace. The seed crystal is preheated on the surface of the mixed melt for 10 minutes, then immersed below the liquid surface, so that the seed crystal is remelted in the mixed melt. The temperature is kept constant for 30 minutes and then rapidly cooled to the saturation temperature of 820℃.

[0056] The temperature is then slowly reduced at a rate of 1℃ / day without rotating the seed crystal rod. Once the crystal has grown to the desired size, it is lifted off the surface of the melt and cooled to room temperature at a rate of 20℃ / h. The crystal is then removed from the furnace to obtain a Ba3La4B3O crystal with dimensions of 36mm×22mm×15mm. 13 Br crystal.

[0057] In the reaction formula, barium carbonate can be replaced by other barium salts such as barium bromide, barium nitrate, barium oxalate, or barium sulfate, or by barium oxide or barium hydroxide. Lanthanum oxide can be replaced by other lanthanum salts such as lanthanum carbonate, lanthanum nitrate, lanthanum bromide, lanthanum oxalate, or lanthanum sulfate, or by lanthanum hydroxide. Boric acid can be replaced by boron oxide.

[0058] Example 3:

[0059] According to the reaction formula: 5Ba(OH)₂ + 1BaBr₂ + 6H₃BO₃ + 4La₂O₃ → 2Ba₃La₄B₃O 13 Br + 14H₂O↑ synthesizes Ba₃La₄B₃O 13 Br compounds:

[0060] Ba(OH)2, BaBr2, H3BO3, and La2O3 were weighed directly in a molar ratio of 5:1:6:4. The weighed raw materials were mixed with the flux BaBr2-H3BO3 in a molar ratio of 1:3, with the molar ratio of BaBr2 to H3BO3 being 1:3. The mixture was placed in an open platinum crucible with a diameter of 80mm and a diameter of 80mm, heated to 900℃, and held at that temperature for 60 hours to obtain a mixed melt. The temperature was then lowered to 880℃.

[0061] The temperature was slowly reduced to room temperature at a rate of 3.5℃ / h, and barium lanthanum bromoborate seed crystals were obtained by spontaneous crystallization.

[0062] The obtained Ba3La4B3O 13 The Br seed crystal is fixed on the seed crystal rod and dropped from the top of the crystal growth furnace. The seed crystal is preheated on the surface of the mixed melt for 15 minutes, then immersed below the liquid surface, so that the seed crystal is remelted in the mixed melt. The temperature is kept constant for 30 minutes and then rapidly cooled to the saturation temperature of 867℃.

[0063] The temperature is then slowly reduced at a rate of 3℃ / day, and the seed crystal crucible is rotated at a speed of 5 rpm. After the crystal grows to the desired size, it is lifted off the surface of the melt and cooled to room temperature at a rate of 1℃ / h. Finally, the crystal is removed from the furnace to obtain a Ba3La4B3O crystal with dimensions of 25mm×24mm×10mm. 13 Br crystal.

[0064] In the reaction formula, barium hydroxide can be replaced by other barium salts such as barium bromide, barium nitrate, barium oxalate, or barium sulfate, or barium oxide or barium hydroxide; lanthanum oxide can be replaced by other lanthanum salts such as lanthanum carbonate, lanthanum nitrate, lanthanum bromide, lanthanum oxalate, or lanthanum sulfate, or lanthanum hydroxide; and boric acid can be replaced by boron oxide.

[0065] Example 4:

[0066] According to the reaction formula: 3BaO + 3H₃BO₃ + 2La₂O₃ + 1NH₄Br↑ → Ba₃La₄B₃O 13 Br + 5H₂O↑ + NH₃↑ synthesize Ba₃La₄B₃O 13 Br compounds:

[0067] BaO, H3BO3, La2O3, and NH4Br were weighed directly in a molar ratio of 3:3:2:1. The weighed raw materials were mixed with the flux PbO-H3BO3 in a molar ratio of 1:3, where the molar ratio of PbO to H3BO3 was 1:3. The mixture was placed in an open platinum crucible with a diameter of 80mm and a diameter of 80mm, heated to 890℃, and held at that temperature for 80 hours to obtain a mixed melt. The temperature was then lowered to 875℃.

[0068] The temperature was slowly reduced to room temperature at a rate of 5℃ / h, and barium lanthanum bromoborate seed crystals were obtained by spontaneous crystallization.

[0069] The obtained Ba3La4B3O 13 The Br seed crystal is fixed on the seed crystal rod and dropped from the top of the crystal growth furnace. The seed crystal is preheated on the surface of the mixed melt for 20 minutes, then immersed below the liquid surface, so that the seed crystal is remelted in the mixed melt. The temperature is kept constant for 5 minutes and then rapidly cooled to the saturation temperature of 860℃.

[0070] Then, the temperature is slowly reduced at a rate of 3℃ / day, and the seed crystal rod is rotated at a speed of 15 rpm. After the crystal grows to the required size, the crystal is removed from the molten surface and cooled to room temperature at a rate of 15℃ / h. Finally, the crystal is removed from the furnace to obtain a Ba3La4B3O crystal with dimensions of 35mm×25mm×20mm. 13 Br crystal.

[0071] In the reaction formula, barium oxide can be replaced by other barium salts such as barium bromide, barium nitrate, barium oxalate, or barium sulfate, or by barium oxide or barium hydroxide. Lanthanum oxide can be replaced by other lanthanum salts such as lanthanum carbonate, lanthanum nitrate, lanthanum bromide, lanthanum oxalate, or lanthanum sulfate, or by lanthanum hydroxide. Boric acid can be replaced by boron oxide.

[0072] Example 5

[0073] According to the reaction formula: 3Ba(OH)₂ + 1NH₄Br + 3H₃BO₃ + 2La₂O₃ → Ba₃La₄B₃O 13 Br + 8H₂O↑ + 1NH₃↑ synthesize Ba₃La₄B₃O 13 Br compounds:

[0074] Ba(OH)2, NH4Br, H3BO3, and La2O3 were weighed directly in a molar ratio of 3:1:3:2. The weighed raw materials were mixed with the flux H3BO3-KBr-Na2CO3 in a molar ratio of 1:2, wherein the molar ratio of H3BO3, KBr, and Na2CO3 was 5:1:3. The mixture was placed in an open platinum crucible with a diameter of 80mm and a diameter of 80mm. The temperature was raised to 850℃ and held for 80 hours to obtain a mixed melt. The temperature was then lowered to 830℃.

[0075] The temperature was slowly reduced to room temperature at a rate of 10℃ / h, and barium lanthanum bromoborate seed crystals were obtained by spontaneous crystallization.

[0076] The obtained Ba3La4B3O 13 The Br seed crystal is fixed on the seed crystal rod and dropped from the top of the crystal growth furnace. The seed crystal is preheated on the surface of the mixed melt for 25 minutes, and then partially immersed in the melt to allow the seed crystal to remelt in the mixed melt. The temperature is kept constant for 25 minutes and then rapidly cooled to the saturation temperature of 820℃.

[0077] The temperature is then lowered at a rate of 5℃ / day, and the seed crystal rod is rotated at 30 rpm. After the crystal grows to the required size, it is lifted off the surface of the melt and cooled to room temperature at a rate of 35℃ / h. Finally, the crystal is removed from the furnace to obtain a Ba3La4B3O crystal with dimensions of 22mm×32mm×20mm. 13 Br crystal.

[0078] In the reaction formula, barium hydroxide can be replaced by other barium salts such as barium bromide, barium nitrate, barium oxalate, or barium sulfate, or barium oxide or barium hydroxide; lanthanum oxide can be replaced by other lanthanum salts such as lanthanum carbonate, lanthanum nitrate, lanthanum bromide, lanthanum oxalate, or lanthanum sulfate, or lanthanum hydroxide; and boric acid can be replaced by boron oxide.

[0079] Example 6

[0080] According to the reaction formula: 5BaO + 6H3BO3 + 4La2O3 + 1BaBr2 → 2Ba3La4B3O 13 Br + 9H₂O↑ synthesizes Ba₃La₄B₃O 13 Br compounds:

[0081] BaO, H3BO3, La2O3, and BaBr2 were weighed directly in a molar ratio of 5:6:4:1. The weighed raw materials were mixed with flux H3BO3-KBr in a molar ratio of 1:4, wherein the molar ratio of H3BO3 to KBr was 3:2. The mixture was placed in an open platinum crucible with a diameter of 80mm and a diameter of 80mm, heated to 900℃, and kept at that temperature for 5 hours to obtain a mixed melt. The temperature was then lowered to 880℃.

[0082] The temperature was slowly reduced to room temperature at a rate of 4.0℃ / h to obtain barium lanthanum bromoborate seed crystals through spontaneous crystallization.

[0083] The obtained Ba3La4B3O 13 The Br seed crystal is fixed on the seed crystal rod and dropped from the top of the crystal growth furnace. The seed crystal is preheated on the surface of the mixed melt for 20 minutes, then immersed below the liquid surface, so that the seed crystal is remelted in the mixed melt. The temperature is kept constant for 25 minutes and then rapidly cooled to the saturation temperature of 865℃.

[0084] Then, the temperature is lowered at a rate of 3℃ / day, and the seed crystal rod is rotated at a speed of 50 rpm. After the crystal grows to the required size, the crystal is removed from the molten surface and cooled to room temperature at a rate of 70℃ / h. Finally, the crystal is removed from the furnace to obtain a Ba3La4B3O crystal with dimensions of 22mm×21mm×16mm. 13 Br crystal.

[0085] In the reaction formula, barium oxide can be replaced by other barium salts such as barium bromide, barium nitrate, barium oxalate, or barium sulfate, or by barium oxide or barium hydroxide. Lanthanum oxide can be replaced by other lanthanum salts such as lanthanum carbonate, lanthanum nitrate, lanthanum bromide, lanthanum oxalate, or lanthanum sulfate, or by lanthanum hydroxide. Boric acid can be replaced by boron oxide.

[0086] Example 7

[0087] According to the reaction formula: 5BaCO3 + 6H3BO3 + 1BaBr2 + 8La(NO3)3·6H2O → 2Ba3La4B3O 13Br + 24NO₂↑ + 57H₂O↑ + 5CO₂↑ + 6O₂↑ synthesize Ba₃La₄B₃O 13 Br compounds:

[0088] BaCO3, H3BO3, BaBr2, and La(NO3)3·6H2O were placed in a mortar in a molar ratio of 5:6:1:8, mixed, and carefully ground. The mixture was then placed into a 100mm×100mm open corundum crucible, pressed tightly, and placed in a muffle furnace. The temperature was slowly raised to 400℃ and held for 4 hours. After cooling, the crucible was removed. At this point, the sample was relatively porous. The sample was then removed, re-ground until homogeneous, and placed back into the crucible. The mixture was then held in a muffle furnace at 950℃ for another 48 hours. Finally, the sample was removed, crushed, and ground in a mortar to obtain Ba3La4B3O. 13 The Br compound was subjected to X-ray diffraction analysis, and the resulting X-ray spectrum was similar to that of lanthanum barium bromoborate (Ba3La4B3O). 13 The X-ray spectra obtained from the Br single crystal structure are consistent;

[0089] The synthesized Ba3La4B3O 13 The Br compound was mixed with the flux H3BO3-PbO-BaBr2 in a molar ratio of 1:4, wherein the molar ratio of H3BO3, PbO and BaBr2 was 5:1:1. The mixture was placed in an open platinum crucible with a diameter of 80 mm × 80 mm, heated to 900 °C, held at that temperature for 50 hours to obtain a mixed melt, and then cooled to 880 °C.

[0090] The temperature was slowly reduced to room temperature at a rate of 4.0℃ / h to obtain barium lanthanum bromoborate seed crystals through spontaneous crystallization.

[0091] The obtained Ba3La4B3O 13 The Br seed crystal is fixed on the seed crystal rod and dropped from the top of the crystal growth furnace. The seed crystal is preheated on the surface of the mixed melt for 20 minutes, then immersed below the liquid surface, so that the seed crystal is remelted in the mixed melt. The temperature is kept constant for 25 minutes and then cooled to the saturation temperature of 850℃.

[0092] Then, the temperature is lowered at a rate of 2℃ / day, and the seed crystal rod is rotated at a speed of 28 rpm. After the crystal grows to the required size, the crystal is removed from the molten surface and cooled to room temperature at a rate of 25℃ / h. Finally, the crystal is removed from the furnace to obtain a Ba3La4B3O crystal with dimensions of 30mm×22mm×15mm. 13 Br crystal.

[0093] In the reaction formula, barium carbonate can be replaced by other barium salts such as barium bromide, barium nitrate, barium oxalate, or barium sulfate, or by barium oxide or barium hydroxide. Lanthanum oxide can be replaced by other lanthanum salts such as lanthanum carbonate, lanthanum nitrate, lanthanum bromide, lanthanum oxalate, or lanthanum sulfate, or by lanthanum hydroxide. Boric acid can be replaced by boron oxide.

[0094] Example 8

[0095] According to the reaction formula: 3BaCO3 + 3H3BO3 + 4La(NO3)3·6H2O + 1NH4Br → Ba3La4B3O 13 Br + 1NH3↑ + 3CO2↑ + 12NO2↑ + 29H2O↑ + 3O2↑ synthesize Ba3La4B3O 13 Br compounds:

[0096] BaCO3, H3BO3, La(NO3)3·6H2O, NH4Br, and O2 were placed in a mortar in a molar ratio of 3:3:4:1:21. The weighed raw materials were mixed with the flux H3BO3-PbO-NaBr-BaBr2 in a molar ratio of 1:1, wherein the molar ratio of H3BO3, PbO, NaBr, and BaBr2 was 5:3:4:1. The mixture was placed in an open platinum crucible with a diameter of 80mm and a diameter of 80mm. The temperature was raised to 890℃ and held for 80 hours to obtain a mixed melt. The temperature was then lowered to 865℃.

[0097] The temperature was slowly reduced to room temperature at a rate of 10℃ / h, and barium lanthanum bromoborate seed crystals were obtained by spontaneous crystallization.

[0098] The obtained Ba3La4B3O 13 The Br seed crystal is fixed on the seed crystal rod and dropped from the top of the crystal growth furnace. The seed crystal is preheated on the surface of the mixed melt for 25 minutes, and then partially immersed in the melt to allow the seed crystal to remelt in the mixed melt. The temperature is kept constant for 25 minutes and then rapidly cooled to the saturation temperature of 840℃.

[0099] The temperature is then lowered at a rate of 5℃ / day, and the seed crystal rod is rotated at 30 rpm. After the crystal grows to the required size, it is lifted off the surface of the melt and cooled to room temperature at a rate of 35℃ / h. Finally, the crystal is removed from the furnace to obtain a Ba3La4B3O crystal with dimensions of 22mm×32mm×20mm. 13 Br crystal.

[0100] In the reaction formula, barium carbonate can be replaced by other barium salts such as barium bromide, barium nitrate, barium oxalate, or barium sulfate, or by barium oxide or barium hydroxide. Lanthanum oxide can be replaced by other lanthanum salts such as lanthanum carbonate, lanthanum nitrate, lanthanum bromide, lanthanum oxalate, or lanthanum sulfate, or by lanthanum hydroxide. Boric acid can be replaced by boron oxide.

[0101] Example 9

[0102] Any Ba3La4B3O obtained in Examples 1-8 13 A frequency multiplier device measuring 5mm × 5mm × 6mm was fabricated from a Br crystal with matching orientation, and then... Figure 2As shown, the laser is positioned at location 3. At room temperature, a Q-switched Nd:YAG laser is used as the light source, with an incident wavelength of 1064 nm. An infrared beam 2 with a wavelength of 1064 nm emitted from the Q-switched Nd:YAG laser 1 is incident on Ba3La4B3O. 13 Br single crystal 3 produces green frequency-doubled light with a wavelength of 532nm, and the output intensity is 6 times that of KDP under the same conditions. The emitted beam 4 contains infrared light with a wavelength of 1064nm and green light with a wavelength of 532nm. After being filtered by filter 5, a green laser with a wavelength of 532nm is obtained.

Claims

1. A compound, barium lanthanum bromoborate, characterized in that, The chemical formula of this compound is Ba3La4B3O 13 Br, crystals belong to the hexagonal crystal system, space group 1. P 63 mc The unit cell parameters are a = 10.7828(6) Å, b = 10.7828(6) Å, c = 7.0412(6) Å, and V = 732.22(14) Å. 3 Its molecular weight is 1287.

93.

2. The method for preparing the compound lanthanum barium bromoborate according to claim 1, characterized in that, Includes the following steps: The compound barium lanthanum bromoborate was prepared by mixing a barium-containing compound, a lanthanum-containing compound, a boron-containing compound, and a bromine-containing compound using a solid-state reaction method. The molar ratio of barium in the barium-containing compound, lanthanum in the lanthanum-containing compound, boron in the boron-containing compound, and bromine in the bromine-containing compound was 2.5-3.3:3.5-4.2:2.5-3.5:0.7-1.

3. The raw materials containing barium, lanthanum, boron, and bromine were mixed evenly, ground, and then pre-calcined in a muffle furnace. After cooling to room temperature, the mixture was removed, ground again, and then calcined in a muffle furnace to obtain the compound barium lanthanum bromoborate.

3. The method for preparing the compound barium lanthanum bromoborate according to claim 2, characterized in that, The barium-containing compound includes at least one of barium hydroxide, barium oxide, and barium salts; The lanthanum-containing compound includes at least one of lanthanum oxide, lanthanum hydroxide, and lanthanum salts; The boron-containing compound is boron oxide, boron hydroxide, and boron salts; The bromine-containing compound is at least one of barium bromide and ammonium bromide.

4. The method for preparing the compound barium lanthanum bromoborate according to claim 3, characterized in that, Barium salts include at least one of barium bromide, barium carbonate, barium sulfate, barium nitrate, barium oxalate, and barium acetate; Lanthanum salts include at least one of lanthanum carbonate, lanthanum nitrate, lanthanum bromide, lanthanum oxalate, and lanthanum sulfate.

5. A nonlinear optical crystal of barium lanthanum bromoborate, characterized in that... The chemical formula is Ba3La4B3O 13 Br, crystals belong to the hexagonal crystal system, space group 1. P 63 mc The unit cell parameters are a = 10.7828(6) Å, b = 10.7828(6) Å, c = 7.0412(6) Å, and V = 732.22(14) Å. 3 Its molecular weight is 1287.

93.

6. The method for preparing the barium lanthanum bromoborate nonlinear optical crystal according to claim 5, characterized in that, Barium lanthanum bromoborate nonlinear optical crystals are grown using either the high-temperature melt method or the Czochralski method.

7. The method according to claim 6, characterized in that, The specific operation is carried out according to the following steps: a. Take the compound barium lanthanum bromoborate prepared by the preparation method according to any one of claims 2-4 or the compound barium lanthanum bromoborate prepared by the preparation method according to any one of claims 2-4 and a flux, heat it to melt to obtain a mixed melt, cool it down or grow it at a constant temperature to prepare the compound barium lanthanum bromoborate crystals. Alternatively, a mixture of barium-containing compounds, lanthanum-containing compounds, boron-containing compounds, and bromine-containing compounds, or a mixture of barium-containing compounds, lanthanum-containing compounds, boron-containing compounds, and bromine-containing compounds with a flux, can be heated to melt to obtain a mixed melt, and then cooled or grown at a constant temperature to prepare barium lanthanum bromoborate crystals. b. Place the crucible containing the mixed melt obtained in step a into a crystal growth furnace, fix the seed crystal on the seed crystal rod, lower the seed crystal to the surface of the mixed melt or into the mixed melt for remelting, and reduce it to the saturation temperature; grow at a lower or constant temperature to prepare the compound lanthanum barium bromoborate crystal.

8. The method according to claim 7, characterized in that... The molar ratio of barium lanthanum bromoborate compound single-phase polycrystalline powder to flux is 1:1-20; or the molar ratio of barium-containing compound, lanthanum-containing compound, boron-containing compound, and bromine-containing compound to flux is 3:4:3:1:1-20; single flux includes one or more of barium oxide, boric acid, barium bromide, sodium bromide, lithium bromide, potassium bromide, lead oxide, sodium carbonate, potassium carbonate, and lithium carbonate; composite flux includes BaBr2-H3BO3, PbO-H3BO3, NaBr-H3BO3, LiBr-H3BO3, Na2CO3-H3BO3, and Li 2CO3-H3BO3, K2CO3-H3BO3, BaBr2-PbO, NaBr-PbO, LiBr-PbO, Na2CO3-PbO, Li2CO3-PbO, K2CO3-PbO, PbO-H3BO3, BaBr2-H 3BO3-PbO, NaBr-H3BO3-PbO, LiBr-H3BO3-PbO, Na2CO3-H3BO3-PbO, Li2CO3-H3BO3-PbO, K2CO3-H3BO3-PbO, LiBr-BaBr2- H3BO3, NaBr-BaBr2-H3BO3, NaBr-LiBr-H3BO3, LiBr-Na2CO3-H3BO3, LiBr-K2CO3-H3BO3, NaBr-Na2CO3-H3BO3, NaBr-K2C O3-H3BO3, KBr-Na2CO3-H3BO3-BaBr2, KBr-Na2CO3-H3BO3, KBr-K2CO3-H3BO3, KBr-K2CO3-H3BO3-BaBr2, NaBr-Na2CO3-H 3BO3, NaBr-Na2CO3-H3BO3-BaBr2, NaBr-LiBr-H3BO3-BaBr2, KBr-LiBr-H3BO3-BaBr2, PbO-H3BO3-BaBr2, K2CO3-PbO-Ba One or more of Br2, NaBr-PbO-BaBr2, NaBr-H3BO3-BaBr2, NaBr-H3BO3-BaBr2, LiBr-H3BO3-BaBr2, LiBr-Na2CO3-H3BO3-BaBr2.

9. The use of the nonlinear optical crystal of barium lanthanum bromoborate according to claim 5, characterized in that... This compound, barium lanthanum bromoborate, is used in nonlinear optical crystals to prepare frequency multipliers, up-frequency converters, down-frequency converters, or optical parametric oscillators.

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