Compound guanidine fluoborate and guanidine fluoborate nonlinear optical crystal and preparation method and use thereof

Abstract

The present invention provides a compound guanidine fluoborate and a guanidine fluoborate nonlinear optical crystal and a preparation method and use thereof. The chemical formula of the compound is [C(NH2)3]3B3O3F6, and the molecular weight is 370.66. The guanidine fluoborate nonlinear optical crystal is prepared by a room temperature solution method, and the molecular weight is 370.66. The crystal belongs to the monoclinic system and the space group is P c, the unit cell parameters are a=8.5366(10), b=11.5066(12), c=9.2274(9), α=90°, β=122.682°, γ=90°, and the unit cell volume is 762.88Å 3 The crystal is grown using a room temperature solution method or a hydrothermal method. The crystal has good chemical stability and can be used as a short-wavelength nonlinear optical crystal in all-solid-state lasers.

Description

Technical Field

[0001] The present invention relates to a compound guanidine fluoborate [C(NH2)3]3B3O3F6 and a guanidine fluoborate [C(NH2)3]3B3O3F6 nonlinear optical crystal as well as a preparation method and application thereof. Background Art

[0002] Ultraviolet lasers, due to their high energy and beam quality, have important applications in lithography, micromachining, optoelectronics, and many other fields. Frequency conversion via nonlinear optical crystals is one of the most effective methods for generating ultraviolet laser light. To date, the only practical short-wavelength nonlinear optical crystals developed by Chinese scientists are β-BaB2O4, LiB3O5, and KBe2BO3F2. However, due to limitations in their crystal structure and other properties, they remain elusive for industrialization to meet the demands of scientific and technological development. β-BaB2O4 crystals have a high birefringence, resulting in a small acceptance angle for phase matching and a large walk-off angle, leading to low frequency-doubled conversion efficiency and poor spot quality when generating laser output. LiB3O5 crystals have a low birefringence, resulting in a minimum phase-matching wavelength of only 276 nm, making direct frequency-doubled generation of 266 nm or shorter wavelengths impossible. KBe2BO3F2 crystals, constrained by intrinsic defects (weak interlayer forces), exhibit a severe layered growth habit, making large-scale crystal growth difficult. Therefore, the preparation and synthesis of new short-wavelength nonlinear optical crystal materials with excellent comprehensive performance is of great significance and practical value. Summary of the Invention

[0003] The present invention aims to provide a compound guanidine fluoborate, the chemical formula of the compound is [C(NH2)3]3B3O3F6, the molecular weight is 370.66, and the room temperature solution method is used.

[0004] Another object of the present invention is to provide a guanidine fluoborate [C(NH2)3]3B3O3F6 nonlinear optical crystal with a molecular weight of 370.66, which belongs to the monoclinic system, has a space group of Pc, and has unit cell parameters of a=8.5366(10), b=11.5066(12), c=9.2274(9), α=90°, β=122.682°, γ=90°, and a unit cell volume of

[0005] Another object of the present invention is to provide a method for preparing guanidine fluoborate [C(NH2)3]3B3O3F6 nonlinear optical crystals, using a room temperature solution method or a hydrothermal method to grow the crystals.

[0006] Another object of the present invention is to provide a use of guanidine fluoborate [C(NH2)3]3B3O3F6 nonlinear optical crystal.

[0007] The compound guanidine fluoborate described in the present invention has a chemical formula of [C(NH2)3]3B3O3F6 and a molecular weight of 370.66. The compound is prepared by a room temperature solution method.

[0008] The preparation method of the compound guanidine fluoborate adopts the room temperature solution method, and the specific operation is carried out according to the following steps:

[0009] A C(NH2)3 compound, a B compound, and a fluorine-containing compound are uniformly mixed in a molar ratio of C(NH2)3:B:F=1:1:2, placed in a clean plastic container, and 20-100 mL of deionized water are added. The mixture is then ultrasonically treated to fully mix and dissolve the mixture. The mixed solution is filtered through filter paper to obtain a mixed solution, and the container is sealed with plastic wrap, which is pierced with several small holes. The container is allowed to stand at a temperature of 40-50°C for 5-20 days to obtain a compound [C(NH2)3]3B3O3F6, wherein the C(NH2)3 compound is C(NH2)3HF2, C(NH2)3Cl, C(NH2)3F, [C(NH2)3]2CO3, and C(NH2)3HCO3; the B compound is H3BO3, HBO2, and B2O3; and the F compound is C(NH2)3HF2, HF, and NH4HF2.

[0010] A guanidine fluoborate nonlinear optical crystal, the chemical formula of the crystal is [C(NH2)3]3B3O3F6, the molecular weight is 370.66, the crystal belongs to the monoclinic system, the space group is Pc, the unit cell parameters are a=8.5366(10), b=11.5066(12), c=9.2274(9), α=90°, β=122.682°, γ=90°, and the unit cell volume is

[0011] The method for preparing the guanidine fluoborate nonlinear optical crystal adopts a room temperature solution method or a hydrothermal method to grow the crystal;

[0012] The specific operation of growing the guanidine fluoborate nonlinear optical crystal by the room temperature solution method is carried out in the following steps:

[0013] a. Evenly mix a C(NH2)3 compound, a B compound, and a fluorine-containing compound at a molar ratio of C(NH2)3:B:F=1:1:2, place the mixture in a clean plastic container, add 20-100 mL of deionized water, and then ultrasonicate to fully mix and dissolve the mixture. Filter the mixture with filter paper to obtain a mixed solution, wherein the C(NH2)3 compound is C(NH2)3HF2, C(NH2)3Cl, C(NH2)3F, [C(NH2)3]2CO3, and C(NH2)3HCO3; the B compound is H3BO3, HBO2, and B2O3; and the F compound is C(NH2)3HF2, HF, and NH4HF2;

[0014] b. Place the mixed solution obtained in step a in a clean plastic container, seal it with weighing paper, place it in a static environment without shaking, pollution, or air convection, poke several small holes in the seal to adjust the evaporation rate of water in the aqueous solution, and let it stand at a temperature of 40-50° C. for 5-20 days;

[0015] c. Waiting for the solution in step b to grow crystal particles at the bottom of the container until the size of the crystal particles no longer changes significantly, thereby obtaining seed crystals;

[0016] d. Select the seed crystal with better quality from step c, suspend it in the mixed solution prepared in step b, and let it stand and grow at a temperature of 40-50° C. for 10-30 days to obtain a [C(NH2)3]3B3O3F6 nonlinear optical crystal;

[0017] The hydrothermal method for growing guanidine fluoborate nonlinear optical crystals is specifically performed in the following steps:

[0018] a. Evenly mix the C(NH2)3 compound, the B compound, and the fluorine-containing compound at a molar ratio of C(NH2)3:B:F=1:1:2, put the mixture into a clean plastic container, add 20-65 mL of water, and stir to mix evenly to obtain a mixed solution; filter the mixture with filter paper to obtain a mixed solution, wherein the C(NH2)3 compound is C(NH2)3HF2, C(NH2)3Cl, C(NH2)3F, [C(NH2)3]2CO3, and C(NH2)3HCO3; the B compound is H3BO3, HBO2, and B2O3; and the F compound is C(NH2)3HF2, HF, and NH4HF2;

[0019] b. Transfer the mixed solution obtained in step a into the polytetrafluoroethylene liner of a 23 ml autoclave, add deionized water as the solvent, and tighten and seal the opening of the autoclave;

[0020] c. Place the autoclave in step b in a thermostat and heat the temperature to 220°C at a rate of 20°C / h, maintain the temperature for 24 hours, and then cool it down to room temperature at a rate of 2°C / h;

[0021] d. Open the high-pressure reactor and obtain millimeter-sized [C(NH2)3]3B3O3F6 nonlinear optical crystals in a colorless clear solution.

[0022] The guanidine fluoborate nonlinear optical crystal is used in preparing 1064nm fundamental frequency light output by an Nd:YAG laser for frequency doubling or frequency tripling harmonic light output.

[0023] The guanidine fluoborate nonlinear optical crystal is used in preparing short-wavelength frequency-doubled light outputs of 193, 266 and 355 nm.

[0024] The guanidine fluoborate nonlinear optical crystal is used in preparing a frequency doubling generator, an up or down frequency converter or an optical parametric oscillator.

[0025] The preparation method of guanidine fluoborate nonlinear optical crystals described herein uses a plastic cup lined with a polytetrafluoroethylene (PTFE) liner or a stainless steel-lined hydrothermal autoclave equipped with a platinum sleeve. When using a plastic cup, the container must first be cleaned with acid, rinsed with deionized water, and air-dried.

[0026] The preparation method of the guanidine fluoborate nonlinear optical crystal of the present invention is adopted to obtain a millimeter-sized [C(NH2)3]3B3O3F6 nonlinear optical crystal. By using a large-sized container and extending the growth period of the crystal, a corresponding large-sized nonlinear optical crystal [C(NH2)3]3B3O3F6 can be obtained. During the growth of the [C(NH2)3]3B3O3F6 nonlinear optical crystal, the crystal is easy to grow, transparent and without wrapping, and has the advantages of fast growth speed, low cost, and easy acquisition of large-sized crystals.

[0027] The large-sized guanidine fluoborate nonlinear optical crystal obtained by the preparation method of the present invention can be used as a nonlinear optical device by orienting the crystal blank according to the crystallographic data of the crystal, cutting the crystal according to the required angle, thickness and cross-sectional size, and polishing the light-transmitting surface of the crystal. The [C(NH2)3]3B3O3F6 nonlinear optical crystal has the advantages of stable physicochemical properties, not being easily deliquesced, and being easy to process and store. BRIEF DESCRIPTION OF THE DRAWINGS

[0028] Figure 1 This is the powder XRD spectrum of the compound [C(NH2)3]3B3O3F6 of the present invention;

[0029] Figure 2 This is a structural diagram of the [[C(NH2)3]3B3O3F6 crystal of the present invention;

[0030] Figure 3 This is a working principle diagram of the nonlinear optical device made of [C(NH2)3]3B3O3F6 crystal of the present invention, where 1 is the laser, 2 is the emitted light beam, 3 is the [C(NH2)3]3B3O3F6 crystal, 4 is the output light beam, and 5 is the filter. DETAILED DESCRIPTION

[0031] The present invention is further described below with reference to the following examples. It should be noted that the following examples are not intended to limit the scope of the present invention, and any improvements made based on the present invention do not violate the spirit of the present invention. Unless otherwise specified, the raw materials and equipment used in the present invention are commercially available.

[0032] Example 1

[0033] According to the reaction formula: 3C(NH2)3HF2+3H3BO3→[C(NH2)3]3B3O3F6+6H2O, the compound [C(NH2)3]3B3O3F6 was synthesized by room temperature solution method:

[0034] C(NH2)3HF2 and H3BO3 were mixed evenly in a molar ratio of 1:1 and placed in a clean plastic container. 80 mL of deionized water was added, followed by ultrasonic treatment to fully mix and dissolve the mixture. The mixed solution was filtered with filter paper, and the container was sealed with plastic wrap. Several small holes were pierced in the seal, and the container was allowed to stand at 40°C for 5 days to obtain a polycrystalline powder of the compound [C(NH2)3]3B3O3F6.

[0035] Example 2

[0036] According to the reaction formula: 3C(NH2)3F+3H3BO3+3HF→[C(NH2)3]3B3O3F6+6H2O, the compound C(NH2)3PO2F2 was synthesized by room temperature solution method:

[0037] C(NH2)3F, H3BO3, and HF were mixed evenly in a molar ratio of 1:1:1 and placed in a clean plastic container. 80 mL of deionized water was added, followed by ultrasonic treatment to fully mix and dissolve the mixture. The mixed solution was filtered with filter paper, and the container was sealed with plastic wrap. Several small holes were pierced in the seal, and the container was allowed to stand at 45°C for 10 days to obtain a polycrystalline powder of the compound C(NH2)3PO2F2.

[0038] Example 3

[0039] According to the reaction formula: 3[C(NH2)3]2CO3+6H3BO3+12HF→2[C(NH2)3]3B3O3F6+15H2O+3CO2, the compound [C(NH2)3]3B3O3F6 was synthesized by room temperature solution method:

[0040] [C(NH2)3]2CO3, H3BO3, and HF were mixed evenly in a molar ratio of 1:2:4 and placed in a clean plastic container. 80 mL of deionized water was added, followed by ultrasonic treatment to fully mix and dissolve the mixture. The mixed solution was filtered with filter paper, and the container was sealed with plastic wrap. Several small holes were pierced in the seal, and the container was allowed to stand at 45°C for 15 days to obtain a polycrystalline powder of the compound [C(NH2)3]3B3O3F6.

[0041] Example 4

[0042] According to the reaction formula: 3C(NH2)3Cl+3H3BO3+6HF→[C(NH2)3]3B3O3F6+6H2O+3HCl, the compound [C(NH2)3]3B3O3F6 was synthesized by room temperature solution method:

[0043] C(NH2)3Cl, H3BO3, and HF were mixed evenly in a molar ratio of 1:1:2 and placed in a clean plastic container. 80 mL of deionized water was added, followed by ultrasonic treatment to fully mix and dissolve the mixture. The mixed solution was filtered with filter paper, and the container was sealed with plastic wrap. Several small holes were pierced in the seal, and the container was allowed to stand at 43°C for 13 days to obtain a polycrystalline powder of the compound [C(NH2)3]3B3O3F6.

[0044] Example 5

[0045] According to the reaction formula: 3C(NH2)3HCO3+3H3BO3+6HF→[C(NH2)3]3B3O3F6+9H2O+3CO2, the compound [C(NH2)3]3B3O3F6 was synthesized by room temperature solution method:

[0046] C(NH2)3HCO3, H3BO3, and HF were mixed evenly in a molar ratio of 1:1:2 and placed in a clean plastic container. 80 mL of deionized water was added, followed by ultrasonic treatment to fully mix and dissolve the mixture. The mixed solution was filtered with filter paper, and the container was sealed with plastic wrap. Several small holes were pierced in the seal, and the container was allowed to stand at 48°C for 17 days to obtain a polycrystalline powder of the compound [C(NH2)3]3B3O3F6.

[0047] Example 6

[0048] According to the reaction formula: 6C(NH2)3F+6H3BO3+3NH4HF2→2[C(NH2)3]3B3O3F6+6NH3+12H2O, the compound [C(NH2)3]3B3O3F6 was synthesized by room temperature solution method:

[0049] C(NH2)3F, H3BO3, and NH4HF2 were mixed evenly in a molar ratio of 2:2:1, placed in a clean plastic container, and 20 mL of deionized water was added. The mixture was then ultrasonically treated to fully mix and dissolve. The mixed solution was filtered with filter paper, and then sealed with plastic wrap. Several small holes were pierced in the seal, and the container was allowed to stand at 50°C for 5 days to obtain a polycrystalline powder of the compound [C(NH2)3]3B3O3F6.

[0050] Example 7

[0051] According to the reaction formula: 3[C(NH2)3]2CO3+6H3BO3+6NH4HF2→2[C(NH2)3]3B3O3F6+3CO2+15H2O+6NH3, the compound [C(NH2)3]3B3O3F6 was synthesized by room temperature solution method:

[0052] Mix [C(NH2)3]2CO3, H3BO3, and NH4HF2 in a molar ratio of 1:2:2. Place the mixture in a clean plastic container and add 50 mL of deionized water. Ultrasonicate until thoroughly mixed and dissolved, then filter through filter paper to obtain a mixed solution. Seal the container with plastic wrap, puncture the seal with several small holes, and let it stand at 40°C for 10 days to obtain a polycrystalline powder of the compound [C(NH2)3]3B3O3F6.

[0053] Example 8

[0054] According to the reaction formula: 6C(NH2)3HCO3+6H3BO3+6NH4HF2→2[C(NH2)3]3B3O3F6+6CO2+18H2O+6NH3, the compound [C(NH2)3]3B3O3F6 was synthesized by room temperature solution method:

[0055] C(NH2)3HCO3, H3BO3, and NH4HF2 were mixed uniformly in a molar ratio of 1:1:1, placed in a clean plastic container, and 80 mL of deionized water was added. The mixture was then ultrasonically treated to ensure thorough mixing and dissolution. The mixed solution was filtered with filter paper, and the container was sealed with plastic wrap. Several small holes were pierced in the seal, and the container was allowed to stand at 46°C for 18 days to obtain a polycrystalline powder of the compound [C(NH2)3]3B3O3F6.

[0056] Example 9

[0057] According to the reaction formula: 3C(NH2)3HF2+3HBO2→[C(NH2)3]3B3O3F6+3H2O, the compound [C(NH2)3]3B3O3F6 was synthesized by room temperature solution method:

[0058] Mix C(NH2)3HF2 and HBO2 in a molar ratio of 1:1, put into a clean plastic container, add 100 mL of deionized water, and then ultrasonicate to fully mix and dissolve. Filter with filter paper to obtain a mixed solution, seal with plastic wrap, poke several small holes in the two seals, and let it stand at 40°C for 20 days to obtain a polycrystalline powder of the compound [C(NH2)3]3B3O3F6.

[0059] Example 10

[0060] According to the reaction formula: 3C(NH2)3HF2+3H3BO3→[C(NH2)3]3B3O3F6+6H2O, [C(NH2)3]3B3O3F6 nonlinear optical crystal was grown by room temperature aqueous solution method:

[0061] a. Mix C(NH2)3HF2 and H3BO3 in a molar ratio of 1:1, place in a clean plastic container, add 20 mL of deionized water, and then ultrasonicate to fully mix and dissolve, and filter with filter paper to obtain a mixed solution;

[0062] b. Place the mixed solution obtained in step a in a clean plastic container, seal it with weighing paper, place it in a static environment without shaking, pollution, or air convection, poke several small holes in the seal to adjust the evaporation rate of water in the aqueous solution, and let it stand at a temperature of 50°C for 5 days;

[0063] c. Waiting for the solution in step b to grow crystal particles at the bottom of the container until the size of the crystal particles no longer changes significantly, thereby obtaining seed crystals;

[0064] d. Select the seed crystal with better quality from step c, suspend it in the mixed solution prepared in step b, and let it grow at 40°C for 10 days to obtain a 3 mm × 3 mm × 1 mm [C(NH2)3]3B3O3F6 nonlinear optical crystal.

[0065] Example 11

[0066] According to the reaction formula: 3C(NH2)3F+3H3BO3+3HF→[C(NH2)3]3B3O3F6+6H2O, [C(NH2)3]3B3O3F6 nonlinear optical crystal was grown by room temperature aqueous solution method:

[0067] a. Mix C(NH2)3F, H3BO3, and HF in a molar ratio of 1:1:1, place in a clean plastic container, add 50 mL of deionized water, and then ultrasonicate to fully mix and dissolve. Filter with filter paper to obtain a mixed solution;

[0068] b. Place the mixed solution obtained in step a in a clean plastic container, seal it with weighing paper, place it in a static environment without shaking, pollution, or air convection, poke several small holes in the seal to adjust the evaporation rate of water in the aqueous solution, and let it stand at a temperature of 42°C for 8 days;

[0069] c. Waiting for the solution in step b to grow crystal particles at the bottom of the container until the size of the crystal particles no longer changes significantly, thereby obtaining seed crystals;

[0070] d. Select the seed crystal with better quality from step c, suspend it in the mixed solution prepared in step b, and let it grow at 42°C for 15 days to obtain a 4 mm × 2 mm × 2 mm [C(NH2)3]3B3O3F6 nonlinear optical crystal.

[0071] Example 12

[0072] According to the reaction formula: 3[C(NH2)3]2CO3+6H3BO3+12HF→2[C(NH2)3]3B3O3F6+15H2O+3CO2, [C(NH2)3]3B3O3F6 nonlinear optical crystal was grown by room temperature aqueous solution method:

[0073] a. Mix [C(NH2)3]2CO3, H3BO3, and HF in a molar ratio of 1:2:4, place in a clean plastic container, add 70 mL of deionized water, and then ultrasonicate to fully mix and dissolve, and filter with filter paper to obtain a mixed solution;

[0074] b. Place the mixed solution obtained in step a in a clean plastic container, seal it with weighing paper, place it in a static environment without shaking, pollution, or air convection, poke several small holes in the seal to adjust the evaporation rate of water in the aqueous solution, and let it stand at 45°C for 10 days;

[0075] c. Waiting for the solution in step b to grow crystal particles at the bottom of the container until the size of the crystal particles no longer changes significantly, thereby obtaining seed crystals;

[0076] d. Select the seed crystal with better quality in step c, suspend it in the mixed solution prepared in step b, and let it stand and grow at 45°C for 20 days to obtain a 4mm×3mm×1mm [C(NH2)3]3B3O3F6 linear optical crystal.

[0077] Example 13

[0078] According to the reaction formula: 3C(NH2)3Cl+3H3BO3+6HF→[C(NH2)3]3B3O3F6+6H2O+3HCl, the C(NH2)3]3B3O3F6 nonlinear optical crystal was grown using the room temperature aqueous solution method:

[0079] a. Mix C(NH2)3Cl, H3BO3, and HF in a molar ratio of 1:1:2, place in a clean plastic container, add 100 mL of deionized water, and then ultrasonicate to fully mix and dissolve. Filter with filter paper to obtain a mixed solution;

[0080] b. Place the mixed solution obtained in step a in a clean plastic container, seal it with weighing paper, place it in a static environment without shaking, pollution, or air convection, poke several small holes in the seal to adjust the evaporation rate of water in the aqueous solution, and let it stand at 40°C for 20 days;

[0081] c. Waiting for the solution in step b to grow crystal particles at the bottom of the container until the size of the crystal particles no longer changes significantly, thereby obtaining seed crystals;

[0082] d. Select the seed crystal with better quality from step c, suspend it in the mixed solution prepared in step b, and let it grow at 40°C for 30 days to obtain a 4 mm × 3 mm × 3 mm C(NH2)3]3B3O3F6 nonlinear optical crystal.

[0083] Example 14

[0084] According to the reaction formula: 3C(NH2)3HCO3+3H3BO3+6HF→[C(NH2)3]3B3O3F6+9H2O+3CO2, [C(NH2)3]3B3O3F6 nonlinear optical crystal was grown by room temperature solution method:

[0085] a. Mix C(NH2)3HCO3, H3BO3, and HF in a molar ratio of 1:1:2, place in a clean plastic container, add 20 mL of deionized water, and then ultrasonicate to fully mix and dissolve, and filter with filter paper to obtain a mixed solution;

[0086] b. Place the mixed solution obtained in step a in a clean plastic container, seal it with weighing paper, place it in a static environment without shaking, pollution, or air convection, poke several small holes in the seal to adjust the evaporation rate of water in the aqueous solution, and let it stand at 50°C for 5 days;

[0087] c. Waiting for the solution in step b to grow crystal particles at the bottom of the container until the size of the crystal particles no longer changes significantly, thereby obtaining seed crystals;

[0088] d. Select the seed crystal with better quality in step c, suspend it in the mixed solution prepared in step b, and let it stand for 10 days at a temperature of 50°C to obtain a 3mm×2mm×2mm [C(NH2)3]3B3O3F6 nonlinear optical crystal.

[0089] Example 15

[0090] According to the reaction formula: 6C(NH2)3F+6H3BO3+3NH4HF2→2[C(NH2)3]3B3O3F6+3NH3+12H2O, [C(NH2)3]3B3O3F6 nonlinear optical crystal was grown by room temperature solution method:

[0091] a. Mix C(NH2)3F, H3BO3, and NH4HF2 in a molar ratio of 2:2:1, place in a clean plastic container, add 30 mL of deionized water, and then ultrasonicate to fully mix and dissolve, and filter with filter paper to obtain a mixed solution;

[0092] b. Place the mixed solution obtained in step a in a clean plastic container, seal it with weighing paper, place it in a static environment without shaking, pollution, or air convection, poke several small holes in the seal to adjust the evaporation rate of water in the aqueous solution, and let it stand at 46°C for 15 days;

[0093] c. Waiting for the solution in step b to grow crystal particles at the bottom of the container until the size of the crystal particles no longer changes significantly, thereby obtaining seed crystals;

[0094] d. Select the seed crystal with better quality from step c, suspend it in the mixed solution prepared in step b, and let it grow at 46°C for 20 days to obtain a 4 mm × 2 mm × 2 mm [C(NH2)3]3B3O3F6 nonlinear optical crystal.

[0095] Example 16

[0096] According to the reaction formula: 3[C(NH2)3]2CO3+6H3BO3+6NH4HF2→2[C(NH2)3]3B3O3F6+3CO2+15H2O+6NH3, [C(NH2)3]3B3O3F6 nonlinear optical crystal was grown by room temperature solution method:

[0097] a. Mix [C(NH2)3]2CO3, H3BO3, and NH4HF2 in a molar ratio of 1:2:2, place in a clean plastic container, add 55 mL of deionized water, and then ultrasonicate to fully mix and dissolve, and filter with filter paper to obtain a mixed solution;

[0098] b. Place the mixed solution obtained in step a in a clean plastic container, seal it with weighing paper, place it in a static environment without shaking, pollution, or air convection, poke several small holes in the seal to adjust the evaporation rate of water in the aqueous solution, and let it stand at 47°C for 12 days;

[0099] c. Waiting for the solution in step b to grow crystal particles at the bottom of the container until the size of the crystal particles no longer changes significantly, thereby obtaining seed crystals;

[0100] d. Select the seed crystal with better quality from step c, suspend it in the mixed solution prepared in step b, and let it grow at 42°C for 14 days to obtain a 3 mm × 2 mm × 2 mm [C(NH2)3]3B3O3F6 nonlinear optical crystal.

[0101] Example 17

[0102] According to the reaction formula: 6C(NH2)3HCO3+6H3BO3+6NH4HF2→2[C(NH2)3]3B3O3F6+6CO2+18H2O+6NH3, [C(NH2)3]3B3O3F6 nonlinear optical crystal was grown by room temperature solution method:

[0103] a. Mix C(NH2)3HCO3, H3BO3, and NH4HF2 in a molar ratio of 1:1:1, place in a clean plastic container, add 60 mL of deionized water, and then ultrasonicate to fully mix and dissolve, and filter with filter paper to obtain a mixed solution;

[0104] b. Place the mixed solution obtained in step a in a clean plastic container, seal it with weighing paper, place it in a static environment without shaking, pollution, or air convection, poke several small holes in the seal to adjust the evaporation rate of water in the aqueous solution, and let it stand at 48°C for 18 days;

[0105] c. Waiting for the solution in step b to grow crystal particles at the bottom of the container until the size of the crystal particles no longer changes significantly, thereby obtaining seed crystals;

[0106] d. Select the seed crystal with better quality from step c, suspend it in the mixed solution prepared in step b, and let it grow at 48°C for 25 days to obtain a 4 mm × 3 mm × 1 mm [C(NH2)3]3B3O3F6 nonlinear optical crystal.

[0107] Example 18

[0108] According to the reaction formula: 3C(NH2)3HF2+3HBO2→[C(NH2)3]3B3O3F6+3H2O, [C(NH2)3]3B3O3F6 nonlinear optical crystal was grown by room temperature solution method:

[0109] a. Mix C(NH2)3HF2 and HBO2 in a molar ratio of 1:1, place in a clean plastic container, add 90 mL of deionized water, and then ultrasonicate to fully mix and dissolve, and filter with filter paper to obtain a mixed solution;

[0110] b. Place the mixed solution obtained in step a in a clean plastic container, seal it with weighing paper, place it in a static environment without shaking, pollution, or air convection, poke several small holes in the seal to adjust the evaporation rate of water in the aqueous solution, and let it stand at 44°C for 12 days;

[0111] c. Waiting for the solution in step b to grow crystal particles at the bottom of the container until the size of the crystal particles no longer changes significantly, thereby obtaining seed crystals;

[0112] d. Select the seed crystal with better quality from step c, suspend it in the mixed solution prepared in step b, and let it grow at 44°C for 13 days to obtain a 3 mm × 2 mm × 2 mm [C(NH2)3]3B3O3F6 nonlinear optical crystal.

[0113] Example 19

[0114] According to the reaction formula: 3C(NH2)3HF2+3H3BO3→[C(NH2)3]3B3O3F6+6H2O, [C(NH2)3]3B3O3F6 nonlinear optical crystal is grown by hydrothermal method:

[0115] a. Mix C(NH2)3HF2 and H3BO3 in a molar ratio of 1:1, put them into a clean plastic container, add 20 mL of water, stir and mix well to obtain a mixed solution; filter with filter paper to obtain a mixed solution;

[0116] b. Transfer the mixed solution obtained in step a into the polytetrafluoroethylene liner of a 23 ml autoclave, add deionized water as the solvent, and tighten and seal the opening of the autoclave;

[0117] c. Place the autoclave in step b in a thermostat and heat the temperature to 220°C at a rate of 20°C / h, maintain the temperature for 24 hours, and then cool it down to room temperature at a rate of 2°C / h;

[0118] d. Open the autoclave and obtain a 0.7 mm × 0.4 mm × 0.3 mm [C(NH2)3]3B3O3F6 nonlinear optical crystal in a colorless clear solution.

[0119] Example 20

[0120] According to the reaction formula: 3C(NH2)3F+3H3BO3+3HF→[C(NH2)3]3B3O3F6+6H2O, the [C(NH2)3]3B3O3F6 nonlinear optical crystal is grown by hydrothermal method:

[0121] a. Mix C(NH2)3F, H3BO3, and HF in a molar ratio of 1:1:1, place in a clean plastic container, add 65 mL of water, stir and mix to obtain a mixed solution; filter with filter paper to obtain a mixed solution;

[0122] b. Transfer the mixed solution obtained in step a into the polytetrafluoroethylene liner of a 23 ml autoclave, add deionized water as the solvent, and tighten and seal the opening of the autoclave;

[0123] c. Place the autoclave in step b in a thermostat and heat the temperature to 220°C at a rate of 20°C / h, maintain the temperature for 24 hours, and then cool it down to room temperature at a rate of 2°C / h;

[0124] d. Open the autoclave and obtain a 0.9 mm × 0.5 mm × 0.4 mm [C(NH2)3]3B3O3F6 nonlinear optical crystal in a colorless clear solution.

[0125] Example 21

[0126] According to the reaction formula: 3[C(NH2)3]2CO3+6H3BO3+12HF→2[C(NH2)3]3B3O3F6+15H2O+3CO2, [C(NH2)3]3B3O3F6 nonlinear optical crystal is grown by hydrothermal method:

[0127] a. Mix [C(NH2)3]2CO3, H3BO3, and HF in a molar ratio of 1:2:4, place in a clean plastic container, add 45 mL of water, stir and mix to obtain a mixed solution; filter with filter paper to obtain a mixed solution;

[0128] b. Transfer the mixed solution obtained in step a into the polytetrafluoroethylene liner of a 23 ml autoclave, add deionized water as the solvent, and tighten and seal the opening of the autoclave;

[0129] c. Place the autoclave in step b in a thermostat and heat the temperature to 220°C at a rate of 20°C / h, maintain the temperature for 24 hours, and then cool it down to room temperature at a rate of 2°C / h;

[0130] d. Open the autoclave and obtain a 0.9 mm × 0.7 mm × 0.5 mm [C(NH2)3]3B3O3F6 nonlinear optical crystal in a colorless clear solution.

[0131] Example 22

[0132] According to the reaction formula: 3C(NH2)3Cl+3H3BO3+6HF→[C(NH2)3]3B3O3F6+6H2O+3HCl, the [C(NH2)3]3B3O3F6 nonlinear optical crystal was grown by hydrothermal method:

[0133] a. Mix C(NH2)3Cl, H3BO3, and HF in a molar ratio of 1:1:2, place in a clean plastic container, add 30 mL of water, stir and mix to obtain a mixed solution; filter with filter paper to obtain a mixed solution;

[0134] b. Transfer the mixed solution obtained in step a into the polytetrafluoroethylene liner of a 23 ml autoclave, add deionized water as the solvent, and tighten and seal the opening of the autoclave;

[0135] c. Place the autoclave in step b in a thermostat and heat the temperature to 220°C at a rate of 20°C / h, maintain the temperature for 24 hours, and then cool it down to room temperature at a rate of 2°C / h;

[0136] d. Open the high-pressure reactor and obtain a 1 mm × 0.8 mm × 0.7 mm [C(NH2)3]3B3O3F6 nonlinear optical crystal in a colorless clear solution.

[0137] Example 23

[0138] The arbitrary [C(NH2)3]3B3O3F6 crystals obtained in Examples 10-22 were processed in matching directions, and the attached Figure 3 As shown, it is placed at position 3. At room temperature, a Q-switched Nd:YAG laser is used as the light source with an incident wavelength of 1064nm. The infrared beam 2 with a wavelength of 1064nm emitted by the Q-switched Nd:YAG laser 1 is incident on the [C(NH2)3]3B3O3F6 single crystal 3, generating green frequency-doubled light with a wavelength of 532nm. The output intensity is about 1 times that of KDP under the same conditions.

Claims

1. A guanidine fluoborate nonlinear optical crystal, characterized in that The chemical formula of the crystal is [C(NH2)3]3B3O3F6, the molecular weight is 370.66, it belongs to the monoclinic system, and the space group is P c, the unit cell parameters are a = 8.5366(10), b = 11.5066(12), c = 9.2274(9), α = 90°, β = 122.682°, γ = 90°, and the unit cell volume is 762.88Å 3 .

2. The method for preparing the guanidine fluoborate nonlinear optical crystal according to claim 1, wherein Crystals are grown using a room temperature solution method or a hydrothermal method; The specific operation of growing the guanidine fluoborate nonlinear optical crystal by the room temperature solution method is carried out in the following steps: a. Evenly mix a C(NH2)3 compound, a B compound, and a fluorine-containing compound at a molar ratio of C(NH2)3:B:F=1:1:2, place the mixture into a clean plastic container, add 20-100 mL of deionized water, and then ultrasonicate the mixture to fully mix and dissolve the mixture. Filter the mixture with filter paper to obtain a mixed solution, wherein the C(NH2)3 compound is C(NH2)3HF2, C(NH2)3Cl, C(NH2)3F, [C(NH2)3]2CO3, and C(NH2)3HCO3; the B compound is H3BO3, HBO2, and B2O3; and the F compound is C(NH2)3HF2, HF, and NH4HF2; b. Place the mixed solution obtained in step a in a clean plastic container, seal it with weighing paper, place it in a static environment without shaking, pollution, or air convection, poke several small holes in the seal to adjust the evaporation rate of water in the aqueous solution, and let it stand at a temperature of 40-50° C. for 5-20 days; c. Waiting for the solution in step b to grow crystal particles at the bottom of the container until the crystal particle size no longer changes significantly, thereby obtaining seed crystals; d. Select the seed crystal with better quality from step c, suspend it in the mixed solution prepared in step b, and let it stand and grow at a temperature of 40-50° C. for 10-30 days to obtain a [C(NH2)3]3B3O3F6 nonlinear optical crystal; The hydrothermal method for growing guanidine fluoborate nonlinear optical crystals is specifically performed in the following steps: a. Evenly mix the C(NH2)3 compound, the B compound, and the fluorine-containing compound at a molar ratio of C(NH2)3:B:F=1:1:2, put the mixture into a clean plastic container, add 20-65 mL of water, and stir to mix evenly to obtain a mixed solution; filter the mixture with filter paper to obtain a mixed solution, wherein the C(NH2)3 compound is C(NH2)3HF2, C(NH2)3Cl, C(NH2)3F, [C(NH2)3]2CO3, and C(NH2)3HCO3; the B compound is H3BO3, HBO2, and B2O3; and the F compound is C(NH2)3HF2, HF, and NH4HF2; b. Transfer the mixed solution obtained in step a into the polytetrafluoroethylene liner of a 23 ml autoclave, add deionized water as the solvent, and tighten and seal the opening of the autoclave; c. Place the autoclave in step b in a thermostat and heat it to 220°C at a rate of 20°C / h, keep the temperature constant for 24 hours, and then cool it down to room temperature at a rate of 2°C / h; d. Open the high-pressure reactor and obtain millimeter-sized [C(NH2)3]3B3O3F6 nonlinear optical crystals in a colorless clear solution.

3. A use of the guanidine fluoborate nonlinear optical crystal according to claim 1 in preparing a second harmonic or a third harmonic output of a 1064 nm fundamental frequency light output by a Nd:YAG laser.

4. Use of the guanidine fluoborate nonlinear optical crystal according to claim 1 in producing short-wavelength frequency-doubled light outputs of 193 nm, 266 nm, and 355 nm.

5. Use of the guanidine fluoborate nonlinear optical crystal according to claim 1 in preparing a frequency doubling generator, an up- or down-frequency converter, or an optical parametric oscillator.

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