Compound guanidine fluoroborate, guanidine fluoroborate nonlinear optical crystal, and preparation method and application of compound guanidine fluoroborate nonlinear optical crystal

Abstract

The invention provides a compound guanidine fluoroborate and a guanidine fluoroborate nonlinear optical crystal as well as a preparation method and application, the chemical formula of the compound is [C (NH2) 3] 3B3O3F6, the molecular weight is 370.66, a room temperature solution method is adopted, the molecular weight of the guanidine fluoroborate nonlinear optical crystal is 370.66, the crystal belongs to a monoclinic system, the space group is Pc, and the cell parameters are as follows: a = 8.5366 (10), b = 11.5066 (12), c = 9.2274 (9), alpha = 90 degrees, beta = 122.682 degrees and gamma = 90 degrees. And the unit cell volume is 762.883. And growing the crystal by adopting 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 an all-solid-state laser.

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] Due to its high energy and high beam quality, ultraviolet lasers have important applications in lithography, micromachining, optoelectronic devices and many other fields. Frequency conversion through nonlinear optical crystals is one of the most effective methods to output ultraviolet lasers. So far, the short-wavelength nonlinear optical crystals currently in practical use are β-BaB2O4, LiB3O5 and KBe2BO3F2 crystals invented by Chinese scientists, but due to the limitations of their crystal structure and some performance, they are still unable to be truly industrialized to meet the needs of scientific and technological development. Among them, the birefringence of β-BaB2O4 crystal is too large, the acceptance angle that meets the phase matching condition is small, and the walk-off angle is large, resulting in low frequency conversion efficiency and poor spot quality when realizing laser output; the birefringence of LiB3O5 crystal is too small, and the shortest phase matching wavelength is only 276nm, and it is impossible to output 266nm or shorter wavelength lasers through direct frequency doubling; KBe2BO3F2 crystal is restricted by intrinsic defects (weak interlayer forces in the structure), the layered growth habit of the crystal is very serious, and it is not easy to grow large-sized crystals. Therefore, it is of great significance and practical value to prepare and synthesize new short-wavelength nonlinear optical crystal materials with excellent comprehensive performance. Summary of the invention

[0003] The object of the present invention is 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, 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

[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 the use of guanidine fluoborate [C(NH2)3]3B3O3F6 nonlinear optical crystal.

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

[0008] The preparation method of the compound guanidine fluoborate adopts a 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 mixed uniformly in a molar ratio of C(NH2)3:B:F=1:1:2, put into a clean plastic container, add 20-100 mL of deionized water, and then perform ultrasonic treatment to fully mix and dissolve, filter with filter paper to obtain a mixed solution, seal with plastic wrap, poke a number of small holes in the seal, and 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, C(NH2)3HCO3; the B compound is H3BO3, HBO2, B2O3; the F compound is C(NH2)3HF2, HF, 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 guanidine fluoborate nonlinear optical crystal by room temperature solution method is carried out in the following steps:

[0013] a. Mix the C(NH2)3 compound, the B compound and the fluorine-containing compound in a molar ratio of C(NH2)3:B:F=1:1:2, put them into a clean plastic container, add 20-100 mL of deionized water, and then treat them with ultrasonic waves to fully mix and dissolve them, and filter them with filter paper to obtain a mixed solution. The C(NH2)3 compound is C(NH2)3HF2, C(NH2)3Cl, C(NH2)3F, [C(NH2)3]2CO3, C(NH2)3HCO3; the B compound is H3BO3, HBO2, B2O3; the F compound is C(NH2)3HF2, HF, 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, pierce a number of small holes in the seal to adjust the evaporation rate of water in the aqueous solution, and leave it 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 in step c, suspend it in the mixed solution prepared in step b, and let it stand and grow for 10-30 days at a temperature of 40-50° C. to obtain [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. 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 them into a clean plastic container, add 20-65mL of water, stir and mix them evenly to obtain a mixed solution; filter 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, C(NH2)3HCO3; the B compound is H3BO3, HBO2, B2O3; the F compound is C(NH2)3HF2, HF, NH4HF2;

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

[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, keep the temperature constant 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 large-sized [C(NH2)3]3B3O3F6 nonlinear optical crystals in the colorless clear solution.

[0022] The guanidine fluoborate nonlinear optical crystal is used in preparing the 1064nm fundamental frequency light output by the Nd:YAG laser for double-frequency or triple-frequency 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 fluoroborate nonlinear optical crystal is used in preparing a frequency doubling generator, an up or down frequency converter or an optical parametric oscillator.

[0025] In the preparation method of the guanidine fluoborate nonlinear optical crystal of the present invention, the container used in the preparation process is a plastic cup, and the inner lining is a hydrothermal kettle lined with polytetrafluoroethylene or a stainless steel lining equipped with a platinum sleeve. When using a plastic cup as a container, the container must be cleaned with acid first, then rinsed with deionized water, and dried.

[0026] By adopting the preparation method of guanidine fluoborate nonlinear optical crystal described in the present invention, a millimeter-sized [C(NH2)3]3B3O3F6 nonlinear optical crystal is obtained. 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 guanidine fluoborate nonlinear optical crystal 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 easy to deliquesce, 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 It 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, wherein 1 is a laser, 2 is an emitted light beam, 3 is a [C(NH2)3]3B3O3F6 crystal, 4 is an output light beam, and 5 is a filter. DETAILED DESCRIPTION

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

[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] Mix C(NH2)3HF2 and H3BO3 in a molar ratio of 1:1 and put them into a clean plastic container. Add 80 mL of deionized water and then treat by ultrasonic to mix and dissolve them thoroughly. Filter with filter paper to obtain a mixed solution. Seal the container with plastic wrap, poke several small holes in the seal, and let it 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 put into a clean plastic container. 80 mL of deionized water was added, and then ultrasonic treatment was performed to fully mix and dissolve. The mixed solution was filtered with filter paper, and the solution was sealed with plastic wrap. Several small holes were pierced in the seal, and the solution 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, put into a clean plastic container, added with 80 mL of deionized water, and then ultrasonicated to fully mix and dissolve, filtered with filter paper to obtain a mixed solution, sealed with plastic wrap, pierced a number of small holes in the seal, and 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 loaded into a clean plastic container. 80 mL of deionized water was added, and then ultrasonic treatment was performed to fully mix and dissolve. The mixed solution was filtered with filter paper, and the sealed container was sealed with plastic wrap. Several small holes were pierced in the sealed container, 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 put into a clean plastic container. 80 mL of deionized water was added, and then ultrasonic treatment was performed to fully mix and dissolve. The mixed solution was filtered with filter paper, and the sealed surface was sealed with plastic wrap. Several small holes were pierced in the seal, and the mixture 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, put into a clean plastic container, added with 20 mL of deionized water, and then ultrasonicated to fully mix and dissolve, filtered with filter paper to obtain a mixed solution, and then sealed with plastic wrap, pierced a number of small holes in the seal, and 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: NH4HF2 in a molar ratio of 1:2:2, put it into a clean plastic container, add 50mL of deionized water, and then ultrasonicate it to mix and dissolve it thoroughly, and filter it with filter paper to obtain a mixed solution. Seal it with plastic wrap, poke several small holes in the seal, 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 evenly in a molar ratio of 1:1:1, put into a clean plastic container, added with 80 mL of deionized water, and then ultrasonicated to fully mix and dissolve, filtered with filter paper to obtain a mixed solution, sealed with plastic wrap, pierced a number of small holes in the seal, and 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 them into a clean plastic container, add 100 mL of deionized water, and then treat them by ultrasonic wave to mix and dissolve them thoroughly. Filter with filter paper to obtain a mixed solution, seal it with plastic wrap, pierce a number of 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, the [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, put them into a clean plastic container, add 20 mL of deionized water, and then treat with ultrasonic wave to mix and dissolve them thoroughly, 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, pierce several small holes in the seal to adjust the evaporation rate of water in the aqueous solution, and leave it at 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 in step c, suspend it in the mixed solution prepared in step b, and let it stand and grow for 10 days at 40°C to obtain a 3mm×3mm×1mm [C(NH2)3]3B3O3F6 nonlinear optical crystal.

[0065] Embodiment 11

[0066] According to the reaction formula: 3C(NH2)3F+3H3BO3+3HF→[C(NH2)3]3B3O3F6+6H2O, the [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, put them into a clean plastic container, add 50 mL of deionized water, and then treat with ultrasonic wave to mix and dissolve them thoroughly, and 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, pierce several small holes in the seal to adjust the evaporation rate of water in the aqueous solution, and leave it at 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 in 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 4mm×2mm×2mm [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, the [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, put them into a clean plastic container, add 70 mL of deionized water, and then treat with ultrasound to fully mix and dissolve them, 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, pierce several small holes in the seal to adjust the evaporation rate of water in the aqueous solution, and leave it 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] Embodiment 13

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

[0079] a. Mix C(NH2)3Cl, H3BO3 and HF in a molar ratio of 1:1:2, put them into a clean plastic container, add 100 mL of deionized water, and then treat with ultrasonic wave to mix and dissolve them thoroughly, and 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, pierce several small holes in the seal to adjust the evaporation rate of water in the aqueous solution, and leave it 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 in step c, suspend it in the mixed solution prepared in step b, and let it stand and grow for 30 days at 40°C to obtain a 4mm×3mm×3mm C(NH2)3]3B3O3F6 nonlinear optical crystal.

[0083] Embodiment 14

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

[0085] a. Mix C(NH2)3HCO3, H3BO3 and HF in a molar ratio of 1:1:2, put them into a clean plastic container, add 20 mL of deionized water, and then treat with ultrasonic wave to mix and dissolve them thoroughly, 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, pierce several small holes in the seal to adjust the evaporation rate of water in the aqueous solution, and leave it 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] Embodiment 15

[0090] According to the reaction formula: 6C(NH2)3F+6H3BO3+3NH4HF2→2[C(NH2)3]3B3O3F6+3NH3+12H2O, the [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, put them into a clean plastic container, add 30 mL of deionized water, and then treat with ultrasonic wave to mix and dissolve them thoroughly, 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, pierce several small holes in the seal to adjust the evaporation rate of water in the aqueous solution, and leave it 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 in step c, suspend it in the mixed solution prepared in step b, and let it stand and grow at 46°C for 20 days to obtain a 4mm×2mm×2mm [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, the [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, put them into a clean plastic container, add 55 mL of deionized water, and then treat with ultrasound to fully mix and dissolve them, 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, pierce several small holes in the seal to adjust the evaporation rate of water in the aqueous solution, and leave it 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 in 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 3mm×2mm×2mm [C(NH2)3]3B3O3F6 nonlinear optical crystal.

[0101] Embodiment 17

[0102] According to the reaction formula: 6C(NH2)3HCO3+6H3BO3+6NH4HF2→2[C(NH2)3]3B3O3F6+6CO2+18H2O+6NH3, the [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, put them into a clean plastic container, add 60 mL of deionized water, and then treat with ultrasound to fully mix and dissolve them, 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, pierce several small holes in the seal to adjust the evaporation rate of water in the aqueous solution, and leave it 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 in 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 4mm×3mm×1mm [C(NH2)3]3B3O3F6 nonlinear optical crystal.

[0107] Embodiment 18

[0108] According to the reaction formula: 3C(NH2)3HF2+3HBO2→[C(NH2)3]3B3O3F6+3H2O, the [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, put them into a clean plastic container, add 90 mL of deionized water, and then treat with ultrasonic wave to mix and dissolve them thoroughly, 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, pierce several small holes in the seal to adjust the evaporation rate of water in the aqueous solution, and leave it 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 in 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 3mm×2mm×2mm [C(NH2)3]3B3O3F6 nonlinear optical crystal.

[0113] Embodiment 19

[0114] According to the reaction formula: 3C(NH2)3HF2+3H3BO3→[C(NH2)3]3B3O3F6+6H2O, the [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 and put them into a clean plastic container, add 20 mL of water, stir and mix 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 high-pressure reactor, add deionized water as a solvent, and tighten and seal the mouth of the reactor;

[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, keep the temperature constant for 24 hours, and then cool it down to room temperature at a rate of 2°C / h;

[0118] d. Open the high-pressure reactor 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] Embodiment 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 and put them into 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 high-pressure reactor, add deionized water as a solvent, and tighten and seal the mouth of the reactor;

[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, keep the temperature constant for 24 hours, and then cool it down to room temperature at a rate of 2°C / h;

[0124] d. Open the high-pressure reactor 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] Embodiment 21

[0126] According to the reaction formula: 3[C(NH2)3]2CO3+6H3BO3+12HF→2[C(NH2)3]3B3O3F6+15H2O+3CO2, the [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 and put them into 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 high-pressure reactor, add deionized water as a solvent, and tighten and seal the mouth of the reactor;

[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, keep the temperature constant for 24 hours, and then cool it down to room temperature at a rate of 2°C / h;

[0130] d. Open the high-pressure reactor 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] Embodiment 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 is grown by hydrothermal method:

[0133] a. Mix C(NH2)3Cl, H3BO3, and HF in a molar ratio of 1:1:2 and put them into 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 high-pressure reactor, add deionized water as a solvent, and tighten and seal the mouth of the reactor;

[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, keep the temperature constant 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] Embodiment 23

[0138] Any [C(NH2)3]3B3O3F6 crystal obtained in Examples 10-22 is processed in a matching direction, 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. The incident wavelength is 1064nm. The infrared light 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 doubled frequency light with a wavelength of 532nm. The output intensity is about 1 times that of KDP under the same conditions.

Claims

1. A compound guanidine fluoborate, characterized in that The compound has the chemical formula [C(NH2)3]3B3O3F6, a molecular weight of 370.66, and is prepared using a room temperature solution method.

2. The method for preparing the compound guanidine fluoborate as claimed in claim 1, characterized in that The room temperature solution method is used, and the specific operation is carried out according to the following steps: The room temperature solution method is used to prepare the compound guanidine fluoborate: A C(NH2)3 compound, a B compound, and a fluorine-containing compound are mixed uniformly in a molar ratio of C(NH2)3:B:F=1:1:2, put into a clean plastic container, add 20-100 mL of deionized water, and then perform ultrasonic treatment to fully mix and dissolve, filter with filter paper to obtain a mixed solution, and then seal with plastic wrap, poke a number of small holes in the seal, and 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, C(NH2)3HCO3; the B compound is H3BO3, HBO2, B2O3; the F compound is C(NH2)3HF2, HF, NH4HF2.

3. A guanidine fluoroborate 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 .

4. The method for preparing the guanidine fluoborate nonlinear optical crystal according to claim 3, characterized in that Growing crystals using room temperature solution method or hydrothermal method; The specific operation of growing guanidine fluoborate nonlinear optical crystal by room temperature solution method is carried out in the following steps: a. Mix the C(NH2)3 compound, the B compound and the fluorine-containing compound in a molar ratio of C(NH2)3:B:F=1:1:2, put them into a clean plastic container, add 20-100 mL of deionized water, and then perform ultrasonic treatment to fully mix and dissolve them, and filter them with filter paper to obtain a mixed solution. The C(NH2)3 compound is C(NH2)3HF2, C(NH2)3Cl, C(NH2)3F, [C(NH2)3]2CO3, C(NH2)3HCO3; the B compound is H3BO3, HBO2, B2O3; the F compound is C(NH2)3HF2, HF, 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, pierce a number of small holes in the seal to adjust the evaporation rate of water in the aqueous solution, and leave it 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 size of the crystal particles no longer changes significantly, thereby obtaining seed crystals; 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 for 10-30 days at a temperature of 40-50° C. to obtain [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. 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 them into a clean plastic container, add 20-65mL of water, stir and mix them evenly to obtain a mixed solution; filter 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, C(NH2)3HCO3; the B compound is H3BO3, HBO2, B2O3; the F compound is C(NH2)3HF2, HF, NH4HF2; b. Transfer the mixed solution obtained in step a into the polytetrafluoroethylene liner of a 23 ml high-pressure reactor, add deionized water as a solvent, and tighten and seal the mouth of the reactor; c. Place the autoclave in step b in a thermostat and heat it to 220°C at a rate of 20°C / h for 24 hours, then cool it down to room temperature at a rate of 2°C / h; d. Open the high-pressure reactor and obtain millimeter-sized large-sized [C(NH2)3]3B3O3F6 nonlinear optical crystals in the colorless clear solution.

5. A use of the guanidine fluoroborate nonlinear optical crystal as claimed in claim 3 in preparing a doubled or tripled harmonic light output of the fundamental frequency light of 1064 nm output by a Nd: YAG laser.

6. Use of the guanidine fluoroborate nonlinear optical crystal as claimed in claim 3 in the preparation of short-wavelength frequency-doubled light outputs of 193 nm, 266 nm and 355 nm.

7. Use of the guanidine fluoroborate nonlinear optical crystal as claimed in claim 3 in preparing a frequency doubling generator, an up or down frequency converter or an optical parametric oscillator.

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