Sodium cesium fluoroborate and sodium cesium fluoroborate nonlinear optical crystals, their preparation methods and applications

Abstract

This invention provides a compound, sodium cesium fluoroborate, and a sodium cesium fluoroborate nonlinear optical crystal, along with their preparation methods and applications. The compound has the chemical formula NaCs7[B3O3F4(OH)]4(H2O)3 and a molecular weight of 1701.16, and is prepared using a room-temperature solution method. The crystal also has the chemical formula NaCs7[B3O3F4(OH)]4(H2O)3 and a molecular weight of 1701.16. This crystal belongs to the monoclinic crystal system and has a space group of [space group missing]. P 21, cell parameters are a =11.5864(15), b =13.463(2), c =12.5958(19), α =90°, β =90°, c =109.697(5)°, unit cell volume is 1849(5) Å 3 The crystal is grown using a room temperature solution method or a hydrothermal method. It has good chemical stability and can be used as a short-wavelength nonlinear optical crystal in all-solid-state lasers.

Description

Technical Field

[0001] This invention relates to a compound sodium cesium fluoroborate NaCs7[B3O3F4(OH)]4(H2O)3 and a sodium cesium fluoroborate NaCs7[B3O3F4(OH)]4(H2O)3 nonlinear optical crystal, its preparation method, and its uses. Background Technology

[0002] With the strong demand for short-wavelength laser sources from modern instruments such as 193nm photolithography, micro- and nano-precision laser processing, and ultra-high energy resolution photoelectron spectrometers and photoelectron emission microscopes, the development of all-solid-state laser sources has become a recent research hotspot in the international laser science community. Short-wavelength nonlinear optical crystals are a crucial component in the development of all-solid-state short-wavelength ultraviolet laser sources.

[0003] Ultraviolet lasers, with their high energy and high beam quality, have important applications in photolithography, microfabrication, optoelectronic devices, and many other fields. Frequency conversion using nonlinear optical crystals is one of the most effective methods for outputting ultraviolet lasers. To date, the practically applicable short-wavelength nonlinear optical crystals are β-BaB₂O₄, LiB₃O₅, and KBe₂BO₃F₂ crystals invented by Chinese scientists. However, due to limitations in their crystal structure and some properties, they cannot yet be truly industrialized to meet the needs of technological development. Specifically, β-BaB₂O₄ crystal has an excessively high birefringence, resulting in a small receiving angle and a large walk-off angle to satisfy the phase-matching condition, leading to low frequency doubling conversion efficiency and poor beam quality when achieving laser output. LiB₃O₅ crystal has a relatively low birefringence, with a minimum phase-matching wavelength of only 276 nm, making it impossible to output 266 nm or shorter wavelength lasers through direct frequency doubling. KBe₂BO₃F₂ crystal is constrained by intrinsic defects (weak interlayer forces in its structure), exhibiting a very severe layered growth habit, making it difficult to grow large-size crystals. Therefore, the preparation and synthesis of novel short-wavelength nonlinear optical crystal materials with excellent comprehensive performance is of great significance and practical value. Summary of the Invention

[0004] The purpose of this invention is to provide a compound, sodium cesium fluoroborate, with the chemical formula NaCs7[B3O3F4(OH)]4(H2O)3 and a molecular weight of 1701.16, prepared by a room temperature solution method.

[0005] Another object of the present invention is to provide a sodium cesium fluoroborate NaCs7[(B3O3F4(OH)]4(H2O)3 nonlinear optical crystal with a molecular weight of 161.06. This crystal belongs to the monoclinic crystal system, space group P21, and has cell parameters a = 11.5864(15), b = 13.463(2), c = 12.5958(19), α = 90°, β = 90°, γ = 109.697(5)°, with a unit cell volume of...

[0006] Another objective of this invention is to provide a method for preparing sodium cesium fluoroborate NaCs7[B3O3F4(OH)]4(H2O)3 nonlinear optical crystals, wherein the crystals are grown using a room temperature solution method or a hydrothermal method.

[0007] Another object of the present invention is to provide the use of sodium cesium fluoroborate NaCs7[B3O3F4(OH)]4(H2O)3 nonlinear optical crystal.

[0008] The present invention discloses a compound, sodium cesium fluoroborate, with the chemical formula NaCs7[B3O3F4(OH)]4(H2O)3 and a molecular weight of 1701.16, which is prepared by room temperature solution method.

[0009] The preparation method of the compound sodium cesium fluoroborate is carried out by room temperature solution method, and the specific operation is as follows: Mix the Na-containing compound, the Cs-containing compound, and the B and F-containing compounds evenly in a molar ratio of Na:Cs:B:F = 1:7:12:16, place them in a clean plastic container, add 20-100 mL of deionized water, and then sonicate to ensure thorough mixing and dissolution. Filter the mixture with filter paper to obtain a mixed solution, seal it with plastic wrap, punch several small holes in the seal, and let it stand at 40-50℃ for 5-20 days to obtain the compound NaCs7[B3O3F4(OH)]4(H2O)3. The Na-containing compounds are NaHF2, NaF, Na2CO3, NaHCO3, and NaOH; the Cs-containing compounds are CsHF2, CsF, Cs2CO3, and CsHCO3; the B-containing compounds are H3BO3, HBO2, and B2O3; and the F-containing compounds are HF and HBF4.

[0010] A sodium cesium fluoroborate nonlinear optical crystal with the chemical formula NaCs7[B3O3F4(OH)]4(H2O)3 and a molecular weight of 1701.16 is described. The crystal belongs to the monoclinic crystal system, space group P21, and has the following cell parameters: a = 11.5864(15), b = 13.463(2), c = 12.5958(19), α = 90°, β = 90°, γ = 109.697(5)°, and a unit cell volume of [missing value].

[0011] The method for preparing the sodium cesium fluoroborate nonlinear optical crystal involves growing the crystal using a room temperature solution method or a hydrothermal method.

[0012] The room-temperature solution method for growing sodium cesium fluoroborate nonlinear optical crystals is performed according to the following steps:

[0013] a. Mix the Na-containing compound, Cs-containing compound, B-containing compound, and F-containing compound evenly in a molar ratio of Na:Cs:B:F = 1:7:12:16. Place the mixture in a clean plastic container, add 20-100 mL of deionized water, and sonicate to ensure thorough mixing and dissolution. Filter to obtain a mixed solution. The Na-containing compound is NaHF2, NaF, Na2CO3, NaHCO3, or NaOH; the Cs-containing compound is CsHF2, CsF, Cs2CO3, or CsHCO3; the B-containing compound is H3BO3, HBO2, or B2O3; and the F-containing compound is HF or HBF4.

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

[0015] c. Wait for crystal particles to grow at the bottom of the container from the solution in step b, until the size of the crystal particles no longer changes significantly, and you will get a seed crystal.

[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 grow at a temperature of 40-50℃ for 10-30 days to obtain NaCs7[B3O3F4(OH)]4(H2O)3 nonlinear optical crystal.

[0017] The hydrothermal growth of the sodium cesium fluoroborate nonlinear optical crystal is carried out according to the following steps:

[0018] a. Using a molar ratio of Na:Cs:B:F = 1:7:12:16, the Na-containing compound, Cs-containing compound, B-containing compound, and F-containing compound are placed in a polytetrafluoroethylene beaker and mixed thoroughly. The mixture is then placed in a clean plastic container, and 20-65 mL of water is added. The mixture is stirred and mixed thoroughly, then filtered to obtain a mixed solution. The Na-containing compound is NaHF2, NaF, Na2CO3, NaHCO3, or NaOH; the Cs-containing compound is CsHF2, CsF, Cs2CO3, or CsHCO3; the B-containing compound is H3BO3, HBO2, or B2O3; and the F-containing compound is HF or HBF4.

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

[0020] c. Place the high-pressure reactor from step b into a constant temperature chamber and then place it in an oven to raise the temperature to 220°C at a rate of 20°C / h, maintain the temperature for 24 hours, and then lower it to room temperature at a rate of 2°C / h.

[0021] d. Open the high-pressure reactor and obtain a large-size NaCs7[B3O3F4(OH)]4(H2O)3 nonlinear optical crystal in the colorless clear solution.

[0022] The sodium cesium fluoroborate nonlinear optical crystal is used in the preparation of second and third harmonic output of the 1064nm fundamental frequency light output by the Nd:YAG laser.

[0023] The use of the sodium cesium fluoroborate nonlinear optical crystal in the preparation of short-wavelength frequency-doubled light output at 266 nm and 355 nm.

[0024] The sodium cesium fluoroborate nonlinear optical crystal is used in the fabrication of frequency multiplier generators, up or down frequency converters, or optical parametric oscillators.

[0025] The method for preparing the sodium cesium fluoroborate nonlinear optical crystal of the present invention uses a plastic cup as the container during the preparation process, with a hydrothermal reactor lined with polytetrafluoroethylene or a stainless steel liner fitted with a platinum sleeve. When using a plastic cup, the container must first be cleaned with acid, then rinsed with deionized water, and then dried.

[0026] The method for preparing sodium cesium fluoroborate nonlinear optical crystals described in this invention yields millimeter-sized NaCs7[B3O3F4(OH)]4(H2O)3 nonlinear optical crystals. By using a large-size container and extending the crystal growth period, correspondingly large-sized NaCs7[B3O3F4(OH)]4(H2O)3 nonlinear optical crystals can be obtained. During the growth of this NaCs7[B3O3F4(OH)]4(H2O)3 nonlinear optical crystal, the crystal grows easily, becomes transparent and unencapsulated, and has advantages such as fast growth rate, low cost, and easy acquisition of large-sized crystals.

[0027] The method for preparing sodium cesium fluoroborate nonlinear optical crystals described in this invention yields large-size NaCs7[B3O3F4(OH)]4(H2O)3 nonlinear optical crystals. Based on the crystallographic data, the crystal blank is oriented, cut to the required angle, thickness, and cross-sectional dimensions, and the light-transmitting surface is polished. The resulting crystal can then be used as a nonlinear optical device. This NaCs7[B3O3F4(OH)]4(H2O)3 nonlinear optical crystal exhibits stable physicochemical properties, is not easily deliquescent, and is easy to process and store. Attached Figure Description

[0028] Figure 1 The XRD pattern of the compound NaCs7[B3O3F4(OH)]4(H2O)3 powder of this invention is shown below.

[0029] Figure 2 This is a structural diagram of the NaCs7[B3O3F4(OH)]4(H2O)3 crystal of the present invention;

[0030] Figure 3 This is a schematic diagram of the working principle of the nonlinear optical device made from NaCs7[B3O3F4(OH)]4(H2O)3 crystal of the present invention. In the diagram, 1 is a laser, 2 is the emitted beam, 3 is the NaCs7[B3O3F4(OH)]4(H2O)3 crystal, 4 is the emitted beam, and 5 is a filter. Detailed Implementation

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

[0032] Example 1

[0033] According to the reaction formula: NaHF2 + 7CsHCO3 + 12H3BO3 + 14HF → NaCs7[B3O3F4(OH)]4(H2O)3 + 24H2O + 7CO2, the compound NaCs7[B3O3F4(OH)]4(H2O)3 was synthesized by room temperature solution method.

[0034] NaHF2, CsHCO3, H3BO3, and HF were mixed evenly in a molar ratio of 1:7:12:14 and placed into a clean plastic container. 80 mL of deionized water was added, and the mixture was then sonicated to ensure thorough mixing and dissolution. The mixture was filtered to obtain a mixed solution, which was then sealed with plastic wrap with several small holes punched in the seal. The solution was left to stand at 45°C for 15 days to obtain polycrystalline powder of compound NaCs7[B3O3F4(OH)]4(H2O)3.

[0035] Example 2

[0036] According to the reaction formula: NaHF2 + 7CsF + 6B2O3 + 7HF + H2O → NaCs7[B3O3F4(OH)]4(H2O)3, the compound NaCs7[B3O3F4(OH)]4(H2O)3 was synthesized by room temperature solution method.

[0037] Mix NaHF2, CsF, B2O3 and HF in a molar ratio of 1:7:6:7 until homogeneous, and place the mixture into a clean plastic container. Add 80 mL of deionized water, then sonicate to ensure thorough mixing and dissolution. Filter to obtain a mixed solution, seal the container with plastic wrap, make several small holes in the seal, and let it stand at 45°C for 15 days to obtain polycrystalline powder of compound NaCs7[B3O3F4(OH)]4(H2O)3.

[0038] Example 3

[0039] According to the reaction formula: 11NaHF2 + 14Cs2CO3 + 48H3BO3 + 42HF → 4NaCs7[B3O3F4(OH)]4(H2O)3 + 7CO2 + 7NaHCO3 + 75H2O, the compound NaCs7[B3O3F4(OH)]4(H2O)3 was synthesized by room temperature solution method.

[0040] Mix NaHF2, Cs2CO3, H3BO3 and HF evenly in a molar ratio of 11:14:48:42 and place the mixture into a clean plastic container. Add 80 mL of deionized water, then sonicate to ensure thorough mixing and dissolution. Filter to obtain a mixed solution, seal the container with plastic wrap, make several small holes in the seal, and let it stand at 45°C for 15 days to obtain polycrystalline powder of compound NaCs7[B3O3F4(OH)]4(H2O)3.

[0041] Example 4

[0042] According to the reaction formula: NaHF2 + 7CsHF2 + 12H3BO3 → NaCs7[B3O3F4(OH)]4(H2O)3 + 17H2O, the compound NaCs7[B3O3F4(OH)]4(H2O)3 was synthesized by room temperature solution method.

[0043] Mix NaHF2, CsHF2, and H3BO3 in a molar ratio of 1:7:12 until homogeneous, and place the mixture into a clean plastic container. Add 80 mL of deionized water, then sonicate to ensure thorough mixing and dissolution. Filter to obtain a mixed solution, seal the container with plastic wrap, make several small holes in the seal, and let it stand at 45°C for 15 days to obtain polycrystalline powder of compound NaCs7[B3O3F4(OH)]4(H2O)3.

[0044] Example 5

[0045] According to the reaction formula: 8NaHF2 + 7CsHCO3 + 12H3BO3 → NaCs7[B3O3F4(OH)]4(H2O)3 + 17H2O + 7NaHCO3, the compound NaCs7[(B3O3F4(OH)]4(H2O)3 was synthesized by room temperature solution method.

[0046] Mix NaHF2, CsHCO3, and H3BO3 in a molar ratio of 8:7:12. Place the mixture in a clean plastic container, add 80 mL of deionized water, and then sonicate to ensure thorough mixing and dissolution. Filter the mixture to obtain a mixed solution. Seal the container with plastic wrap, making several small holes in the seal. Let it stand at 45°C for 15 days to obtain the polycrystalline powder of compound NaCs7[(B3O3F4(OH)]4(H2O)3.

[0047] Example 6

[0048] According to the reaction formula: NaHF2 + 7CsHCO3 + 6B2O3 + 14HF → NaCs7[B3O3F4(OH)]4(H2O)3 + 7CO2 + 6H2O, the compound NaCs7[B3O3F4(OH)]4(H2O)3 was synthesized by room temperature solution method.

[0049] NaF, CsHCO3, B2O3, and HF were mixed evenly in a molar ratio of 1:7:6:14 and placed in a clean plastic container. 20 mL of deionized water was added, and the mixture was ultrasonically treated to ensure thorough mixing and dissolution. The mixture was then filtered to obtain a mixed solution. The container was sealed with plastic wrap, and several small holes were punched in the seal. The solution was left to stand at 50°C for 5 days to obtain polycrystalline powder of compound NaCs7[B3O3F4(OH)]4(H2O)3.

[0050] Example 7

[0051] According to the reaction formula: NaHF2 + 7CsF + 12HBO2 + 7HF → NaCs7[B3O3F4(OH)]4(H2O)3 + 5H2O, the compound NaCs7[B3O3F4(OH)]4(H2O)3 was synthesized by room temperature solution method.

[0052] Mix NaHF2, CsF, HBO2, and HF evenly in a molar ratio of 1:7:12:7, place the mixture in a clean plastic container, add 50 mL of deionized water, and then sonicate to ensure thorough mixing and dissolution. Filter the mixture to obtain a mixed solution, seal it with plastic wrap, make several small holes in the seal, and let it stand at 40°C for 10 days to obtain polycrystalline powder of compound NaCs7[B3O3F4(OH)]4(H2O)3.

[0053] Example 8

[0054] According to the reaction formula: NaF + 7CsF + 12H3BO3 + 8HF → NaCs7[B3O3F4(OH)]4(H2O)3 + 17H2O, the compound NaCs7[B3O3F4(OH)]4(H2O)3 was synthesized by room temperature solution method.

[0055] Mix NaF, CsF, H3BO3, and HF in a molar ratio of 1:7:12:8 until homogeneous. Place the mixture in a clean plastic container, add 80 mL of deionized water, and then sonicate to ensure thorough mixing and dissolution. Filter the mixture to obtain a mixed solution, seal it with plastic wrap, make several small holes in the seal, and let it stand at 45°C for 15 days to obtain polycrystalline powder of compound NaCs7[B3O3F4(OH)]4(H2O)3.

[0056] Example 9

[0057] According to the reaction formula: NaF + 7CsF + 6B₂O₃ + 8HF → NaCs₇[B₃O₃F₄(OH)]₄(H₂O)₃ + H₂O, the compound NaCs₇[B₃O₃F₄(OH)]₄(H₂O)₃ was synthesized by a room temperature solution method.

[0058] Mix NaF, CsF, B2O3 and HF in a molar ratio of 1:7:6:8 until homogeneous. Place the mixture in a clean plastic container, add 100 mL of deionized water, and then sonicate to ensure thorough mixing and dissolution. Filter the mixture to obtain a mixed solution, seal it with plastic wrap, make several small holes in the seal, and let it stand at 40°C for 20 days to obtain polycrystalline powder of compound NaCs7[B3O3F4(OH)]4(H2O)3.

[0059] Example 10

[0060] According to the reaction formula: NaF + 7CsF + 12HBO2 + 8HF → NaCs7[B3O3F4(OH)]4(H2O)3 + 5H2O, the compound NaCs7[B3O3F4(OH)]4(H2O)3 was synthesized by a room temperature solution method.

[0061] Mix NaF, CsF, HBO2, and HF in a molar ratio of 1:7:12:8 until homogeneous. Place the mixture in a clean plastic container, add 70 mL of deionized water, and then sonicate to ensure thorough mixing and dissolution. Filter the mixture to obtain a mixed solution, seal it with plastic wrap, make several small holes in the seal, and let it stand at 40°C for 18 days to obtain polycrystalline powder of compound NaCs7[B3O3F4(OH)]4(H2O)3.

[0062] Example 11

[0063] According to the reaction formula: NaF + 7CsF + 10H3BO3 + 2HBF4 → NaCs7[B3O3F4(OH)]4(H2O)3 + 11H2O, the compound NaCs7[B3O3F4(OH)]4(H2O)3 was synthesized by room temperature solution method.

[0064] Mix NaF, CsF, H3BO3, and HBF4 in a molar ratio of 1:7:10:2 until homogeneous. Place the mixture in a clean plastic container, add 70 mL of deionized water, and then sonicate to ensure thorough mixing and dissolution. Filter the mixture to obtain a mixed solution, seal it with plastic wrap, make several small holes in the seal, and let it stand at 40°C for 18 days to obtain polycrystalline powder of compound NaCs7[B3O3F4(OH)]4(H2O)3.

[0065] Example 12

[0066] Based on the reaction formula: 8NaOH + 56CsF + 39H3BO3 + 18HBF4 + 27H2O → 8NaCs7[B3O3F4(OH)]4(H2O)3, the nonlinear optical crystal NaCs7[B3O3F4(OH)]4(H2O)3 was grown using the room temperature aqueous solution method.

[0067] a. Mix NaOH, CsF, H3BO3 and HBF4 evenly in a molar ratio of 8:56:39:18, put them into a clean plastic container, add 20mL of deionized water, then sonicate to fully mix and dissolve, filter 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, and place it in a static environment without shaking, pollution, or air convection. Make several small holes in the seal to adjust the evaporation rate of the water in the aqueous solution. Let it stand at 40°C for 20 days.

[0069] c. Wait for crystal particles to grow at the bottom of the container from the solution in step b, until the size of the crystal particles no longer changes significantly, and you will get a seed crystal.

[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 40℃ for 30 days to obtain a 4mm×3mm×1mm NaCs7[B3O3F4(OH)]4(H2O)3 nonlinear optical crystal.

[0071] Example 18

[0072] Based on the reaction formula: 4NaOH + 28CsF + 39HBO2 + 9HBF4 → 4NaCs7[B3O3F4(OH)]4(H2O)3 + 7H2O, the nonlinear optical crystal NaCs7[B3O3F4(OH)]4(H2O)3 was grown using the room temperature aqueous solution method.

[0073] a. Mix NaOH, CsF, HBO2 and HBF4 evenly in a molar ratio of 4:28:39:9, put them into a clean plastic container, add 50mL of deionized water, then sonicate to fully mix and dissolve, filter 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, and place it in a static environment without shaking, pollution, or air convection. Make several small holes in the seal to adjust the evaporation rate of the water in the aqueous solution. Let it stand at 42°C for 10 days.

[0075] c. Wait for crystal particles to grow at the bottom of the container from the solution in step b, until the size of the crystal particles no longer changes significantly, and you will get a seed crystal.

[0076] 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℃ for 10 days to obtain a 4mm×2mm×2mm NaCs7[B3O3F4(OH)]4(H2O)3 nonlinear optical crystal.

[0077] Example 19

[0078] According to the reaction formula: 4NaOH + 28CsF + 39H3BO3 + 9HBF4 → 4NaCs7[B3O3F4(OH)]4(H2O)3 + 45H2O, the nonlinear optical crystal NaCs7[B3O3F4(OH)]4(H2O)3 was grown using the room temperature aqueous solution method.

[0079] a. Mix NaOH, CsF, H3BO3 and HBF4 evenly in a molar ratio of 4:28:39:9, put them into a clean plastic container, add 80mL of deionized water, then sonicate to fully mix and dissolve, filter 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, and place it in a static environment without shaking, pollution, or air convection. Make several small holes in the seal to adjust the evaporation rate of the water in the aqueous solution, and let it stand at 50°C for 5 days.

[0081] c. Wait for crystal particles to grow at the bottom of the container from the solution in step b, until the size of the crystal particles no longer changes significantly, and you will get a seed crystal.

[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 50℃ for 10 days to obtain a 3mm×2mm×1mm NaCs7[B3O3F4(OH)]4(H2O)3 nonlinear optical crystal.

[0083] Example 20

[0084] Based on the reaction formula: Na₂CO₃ + 14CsF + 24H₃BO₃ + 18HF → 2NaCs₇[B₃O₃F₄(OH)]₄(H₂O)₃ + 35H₂O + CO₂, the nonlinear optical crystal NaCs₇[B₃O₃F₄(OH)]₄(H₂O)₃ is grown using a room temperature aqueous solution method.

[0085] a. Mix Na2CO3, CsF, H3BO3 and HF evenly in a molar ratio of 1:14:24:18, put them into a clean plastic container, add 100mL of deionized water, and then sonicate to fully mix and dissolve. Filter the mixture 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, and place it in a static environment without shaking, pollution, or air convection. Make several small holes in the seal to adjust the evaporation rate of water in the aqueous solution. Let it stand at 40-50℃ for 5-20 days.

[0087] c. Wait for crystal particles to grow at the bottom of the container from the solution in step b, until the size of the crystal particles no longer changes significantly, and you will get a seed crystal.

[0088] 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 a temperature of 40-50℃ for 10-30 days to obtain a 4mm×3mm×3mm NaCs7[B3O3F4(OH)]4(H2O)3 nonlinear optical crystal.

[0089] Example 21

[0090] Based on the reaction formula: Na₂CO₃ + 14CsF + 24HBO₂ + 18HF → 2NaCs₇[B₃O₃F₄(OH)]₄(H₂O)₃ + 11H₂O + CO₂, the nonlinear optical crystal NaCs₇[B₃O₃F₄(OH)]₄(H₂O)₃ is grown using the room temperature solution method.

[0091] a. Mix Na2CO3, CsF, HBO2, and HF evenly in a molar ratio of 1:14:24:18, place the mixture in a clean plastic container, add 30 mL of deionized water, and then sonicate to ensure thorough mixing and dissolution. Filter the mixture 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, and place it in a static environment without shaking, pollution, or air convection. Make several small holes in the seal to adjust the evaporation rate of the water in the aqueous solution. Let it stand at 45°C for 15 days.

[0093] c. Wait for crystal particles to grow at the bottom of the container from the solution in step b, until the size of the crystal particles no longer changes significantly, and you will get a seed crystal.

[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 45℃ for 20 days to obtain a 3mm×2mm×1mm NaCs7[B3O3F4(OH)]4(H2O)3 nonlinear optical crystal.

[0095] Example 22

[0096] Based on the reaction formula: Na₂CO₃ + 14CsF + 12B₂O₃ + 18HF + H₂O → 2NaCs₇[B₃O₃F₄(OH)]₄(H₂O)₃, the nonlinear optical crystal NaCs₇[B₃O₃F₄(OH)]₄(H₂O)₃ is grown using a room temperature solution method.

[0097] a. Mix Na2CO3, Cs, B2O3 and HF evenly in a molar ratio of 1:14:12:18, put them into a clean plastic container, add 100mL of deionized water, then sonicate to fully mix and dissolve, filter 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, and place it in a static environment without shaking, pollution, or air convection. Make 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 17 days.

[0099] c. Wait for crystal particles to grow at the bottom of the container from the solution in step b, until the size of the crystal particles no longer changes significantly, and you will get a seed crystal.

[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 46℃ for 22 days to obtain a 4mm×2mm×2mm NaCs7[B3O3F4(OH)]4(H2O)3 nonlinear optical crystal.

[0101] Example 23

[0102] Based on the reaction formula: 2Na₂CO₃ + 28CsF + 39H₃BO₃ + 9HBF₄ → 4NaCs₇[B₃O₃F₄(OH)]₄(H₂O)₃ + 43H₂O + CO₂, the nonlinear optical crystal NaCs₇[B₃O₃F₄(OH)]₄(H₂O)₃ is grown using a room temperature solution method.

[0103] a. Mix Na2CO3, CsF, H3BO3 and HBF4 evenly in a molar ratio of 2:28:39:9, put them into a clean plastic container, add 80mL of deionized water, then sonicate to fully mix and dissolve, filter 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, and place it in a static environment without shaking, pollution, or air convection. Make several small holes in the seal to adjust the evaporation rate of the water in the aqueous solution, and let it stand at 48°C for 18 days.

[0105] c. Wait for crystal particles to grow at the bottom of the container from the solution in step b, until the size of the crystal particles no longer changes significantly, and you will get a seed crystal.

[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℃ for 28 days to obtain a 3mm×2mm×2mm NaCs7[B3O3F4(OH)]4(H2O)3 nonlinear optical crystal.

[0107] Example 24

[0108] Based on the reaction formula: 2Na₂CO₃ + 28CsF + 39HBO₂ + 9HBF₄ → 4NaCs₇[B₃O₃F₄(OH)]₄(H₂O)₃ + 4H₂O + 2CO₂, the nonlinear optical crystal NaCs₇[B₃O₃F₄(OH)]₄(H₂O)₃ is grown using a room temperature solution method.

[0109] a. Mix Na2CO3, CsF, HBO2 and HBF4 evenly in a molar ratio of 2:28:39:9, put them into a clean plastic container, add 30mL of deionized water, then sonicate to fully mix and dissolve, filter 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, and place it in a static environment without shaking, pollution, or air convection. Make several small holes in the seal to adjust the evaporation rate of water in the aqueous solution, and let it stand at 43°C for 8 days.

[0111] c. Wait for crystal particles to grow at the bottom of the container from the solution in step b, until the size of the crystal particles no longer changes significantly, and you will get a seed crystal.

[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 43℃ for 12 days to obtain a 4mm×3mm×3mm NaCs7[B3O3F4(OH)]4(H2O)3 nonlinear optical crystal.

[0113] Example 25

[0114] Based on the reaction formula: 4Na₂CO₃ + 56CsF + 39B₂O₃ + 18HBF₄ + 31H₂O → 8NaCs₇[B₃O₃F₄(OH)]₄(H₂O)₃ + 4CO₂, the nonlinear optical crystal NaCs₇[B₃O₃F₄(OH)]₄(H₂O)₃ is grown using a room temperature solution method.

[0115] a. Mix Na2CO3, CsF, B2O3 and HBF4 evenly in a molar ratio of 4:56:39:18, put them into a clean plastic container, add 40mL of deionized water, then sonicate to fully mix and dissolve, filter to obtain a mixed solution;

[0116] b. Place the mixed solution obtained in step a in a clean plastic container, seal it with weighing paper, and place it in a static environment without shaking, pollution, or air convection. Make several small holes in the seal to adjust the evaporation rate of water in the aqueous solution. Let it stand at 46°C for 11 days.

[0117] c. Wait for crystal particles to grow at the bottom of the container from the solution in step b, until the size of the crystal particles no longer changes significantly, and you will get a seed crystal.

[0118] 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℃ for 26 days to obtain a 3mm×2mm×2mm NaCs7[B3O3F4(OH)]4(H2O)3 nonlinear optical crystal.

[0119] Example 26

[0120] Based on the reaction formula: NaHCO3 + 7CsF + 12H3BO3 + 9HF → NaCs7[B3O3F4(OH)]4(H2O)3 + 18H2O + CO2, the nonlinear optical crystal NaCs7[B3O3F4(OH)]4(H2O)3 is grown using a hydrothermal method.

[0121] a. Mix NaHCO3, CsF, H3BO3 and HF in a polytetrafluoroethylene beaker at a molar ratio of 1:7:12:9 until homogeneous. Transfer the mixture to a clean plastic container, add 20 mL of water, and stir until homogeneous. Filter the mixture through filter paper to obtain a mixed solution.

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

[0123] c. Place the high-pressure reactor from step b into a constant temperature chamber and then place it in an oven to raise the temperature to 220°C at a rate of 20°C / h, maintain the temperature for 24 hours, and then lower it to room temperature at a rate of 2°C / h.

[0124] d. Open the high-pressure reactor and obtain a 0.7mm×0.4mm×0.3mm NaCs7[B3O3F4(OH)]4(H2O)3 nonlinear optical crystal from the colorless clear solution.

[0125] Example 27

[0126] Based on the reaction formula: NaHCO3 + 7CsHF2 + 12H3BO3 + 2HF → NaCs7[B3O3F4(OH)]4(H2O)3 + 18H2O + CO2, the nonlinear optical crystal NaCs7[B3O3F4(OH)]4(H2O)3 is grown using a hydrothermal method.

[0127] a. Mix NaHCO3, CsHF2, H3BO3 and HF in a polytetrafluoroethylene beaker at a molar ratio of 1:7:12:2. Place the mixture in a clean plastic container, add 25 mL of water, stir and mix well to obtain a mixed liquid. Filter the mixture with filter paper to obtain a mixed solution.

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

[0129] c. Place the high-pressure reactor from step b into a constant temperature chamber and then place it in an oven to raise the temperature to 220°C at a rate of 20°C / h, maintain the temperature for 24 hours, and then lower it to room temperature at a rate of 2°C / h.

[0130] d. Open the high-pressure reactor and obtain a 0.9mm×0.5mm×0.4mm NaCs7[B3O3F4(OH)]4(H2O)3 nonlinear optical crystal from the colorless clear solution.

[0131] Example 28

[0132] Reaction formula: 2NaHCO3 + 7Cs2CO3 + 24H3BO3 + 32HF → 2NaCs7[B3O3F4(OH)]4(H2O)3 + 43H2O + 9CO2. NaCs7[B3O3F4(OH)]4(H2O)3 nonlinear optical crystal is grown using a hydrothermal method.

[0133] a. Mix NaHCO3, Cs2CO3, H3BO3 and HF in a polytetrafluoroethylene beaker at a molar ratio of 2:7:24:32 until homogeneous. Transfer the mixture to a clean plastic container, add 40 mL of water, stir and mix until homogeneous to obtain a mixed solution. Filter the mixture through filter paper to obtain a mixed solution.

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

[0135] c. Place the high-pressure reactor from step b into a constant temperature chamber and then place it in an oven to raise the temperature to 220°C at a rate of 20°C / h, maintain the temperature for 24 hours, and then lower it to room temperature at a rate of 2°C / h.

[0136] d. Open the high-pressure reactor and obtain a 1mm×0.7mm×0.5mm NaCs7[B3O3F4(OH)]4(H2O)3 nonlinear optical crystal from the colorless clear solution.

[0137] Example 29

[0138] Based on the reaction formula: NaHCO3 + 7CsHCO3 + 12H3BO3 + 16HF → NaCs7[B3O3F4(OH)]4(H2O)3 + 25H2O + 8CO2, the nonlinear optical crystal NaCs7[B3O3F4(OH)]4(H2O)3 is grown using a hydrothermal method.

[0139] a. Mix NaHCO3, CsHCO3, H3BO3 and HF in a polytetrafluoroethylene beaker at a molar ratio of 1:7:12:16 until homogeneous. Transfer the mixture to a clean plastic container, add 45 mL of water, stir and mix until homogeneous to obtain a mixed solution. Filter the mixture through filter paper to obtain a mixed solution.

[0140] b. Transfer the mixed solution obtained in step a into the polytetrafluoroethylene liner of a 23ml high-pressure reactor, add deionized water as a solvent, and tighten and seal the reactor opening.

[0141] c. Place the high-pressure reactor from step b into a constant temperature chamber and then place it in an oven to raise the temperature to 220°C at a rate of 20°C / h, maintain the temperature for 24 hours, and then lower it to room temperature at a rate of 2°C / h.

[0142] d. Open the high-pressure reactor and obtain a 1mm×0.7mm×0.6mm NaCs7[B3O3F4(OH)]4(H2O)3 nonlinear optical crystal from the colorless clear solution.

[0143] Example 30

[0144] The arbitrary NaCs7[B3O3F4(OH)]4(H2O)3 crystals obtained in Examples 12-29 were processed according to matching directions, and then processed according to the attached... Figure 3 As shown, the crystal is positioned at position 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 is emitted from the Q-switched Nd:YAG laser 1 and incident on the NaCs7[B3O3F4(OH)]4(H2O)3 single crystal 3, producing green frequency-doubled light with a wavelength of 532 nm. The output intensity is approximately 1 times that of KDP under the same conditions.

Claims

1. A sodium cesium fluoroborate nonlinear optical crystal, characterized in that... The crystal has the chemical formula NaCs7[B3O3F4(OH)]4(H2O)3, a molecular weight of 1701.16, and belongs to the monoclinic crystal system with space group [missing information]. P 21, cell parameters are a =11.5864(15), b =13.463(2), c = 12.5958(19), α = 90°, β = 90°, γ = 109.697(5)°, unit cell volume is 1849(5) Å 3 .

2. The method for preparing the sodium cesium fluoroborate nonlinear optical crystal as described in claim 1, characterized in that... Crystals are grown using either room temperature solution method or hydrothermal method; The room-temperature solution method for growing sodium cesium fluoroborate nonlinear optical crystals is performed according to the following steps: a. Mix the Na-containing compound, Cs-containing compound, B-containing compound, and F-containing compound evenly in a molar ratio of Na:Cs:B:F = 1:7:12:

16. Place the mixture in a clean plastic container, add 20-100 mL of deionized water, and sonicate to ensure thorough mixing and dissolution. Filter to obtain a mixed solution. The Na-containing compound is NaHF2, NaF, Na2CO3, NaHCO3, or NaOH; the Cs-containing compound is CsHF2, CsF, Cs2CO3, or CsHCO3; the B-containing compound is H3BO3, HBO2, or B2O3; and the F-containing compound is HF or HBF4. b. Place the mixed solution obtained in step a in a clean plastic container, seal it with weighing paper, and place it in a static environment without shaking, pollution, or air convection. Make several small holes in the seal to adjust the evaporation rate of the water in the aqueous solution. Let it stand at a temperature of 40-50℃ for 5-20 days. c. Wait for crystal particles to grow at the bottom of the container from the solution in step b, until the size of the crystal particles no longer changes significantly, and you will get a seed crystal. 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 a temperature of 40-50℃ for 10-30 days to obtain NaCs7[B3O3F4(OH)]4(H2O)3 nonlinear optical crystal. The hydrothermal growth of the sodium cesium fluoroborate nonlinear optical crystal is carried out according to the following steps: A mixture of Na-containing, Cs-containing, B-containing, and F-containing compounds was prepared by mixing them thoroughly in a polytetrafluoroethylene beaker at a molar ratio of Na:Cs:B:F = 1:7:12:

16. The mixture was then placed in a clean plastic container, and 20-65 mL of water was added. The mixture was stirred until homogeneous, filtered, and the resulting solution was obtained. The Na-containing compound was NaHF2, NaF, Na2CO3, NaHCO3, or NaOH; the Cs-containing compound was CsHF2, CsF, Cs2CO3, or CsHCO3; the B-containing compound was H3BO3, HBO2, or B2O3; and the F-containing compound was HF or HBF4. The mixed solution obtained in step a was transferred into the polytetrafluoroethylene liner of a 23 ml high-pressure reactor, deionized water was added as a solvent, and the reactor opening was tightened and sealed. The high-pressure reactor from step b was placed in a constant temperature chamber and then placed in an oven. The temperature was raised to 220°C at a rate of 20°C / h and held for 24 hours. Then the temperature was lowered to room temperature at a rate of 2°C / h. When the high-pressure reactor is opened, a large-sized NaCs7[B3O3F4(OH)]4(H2O)3 nonlinear optical crystal with a diameter of millimeters is obtained from the colorless, clear solution.

3. The use of the sodium cesium fluoroborate nonlinear optical crystal as described in claim 1 in preparing second and third harmonic output of the 1064 nm fundamental frequency light output by an Nd:YAG laser.

4. The use of the sodium cesium fluoroborate nonlinear optical crystal as described in claim 1 in the preparation of short-wavelength frequency-doubled light output at 266 nm and 355 nm.

5. The use of the sodium cesium fluoroborate nonlinear optical crystal as described in claim 1 in the fabrication of a frequency multiplier, an up or down frequency converter, or an optical parametric oscillator.

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