Series of malonate borate nonlinear optical crystals, methods of making and uses thereof

Abstract

This invention relates to a series of malonate borate nonlinear optical crystals, their preparation methods, and applications. The general molecular formula of this series of compounds is AM[C3H2O4]B(OH)3(H2O). x Where A = K, Rb, Cs; M = K, Rb, Cs, x = 0, 1, molecular weight is 242.08–436.72, prepared by room temperature solution method, orthorhombic crystal system, space group P 212121 (No. 19), with cell parameters a = 6.6168(11) - 7.256(3) Å, b = 9.574(5) - 10.271(3) Å, c = 13.0172(12) - 13.984(5) Å. α =90, β =90, gamma =90, Z =4, V=851.3(4)-1042.2(7)Å 3 The series of malonate borate nonlinear optical crystals obtained by this method have advantages such as a wide transmission band, stable physicochemical properties, moderate mechanical hardness, resistance to breakage, and ease of cutting, polishing, and storage. They can withstand 1064nm infrared light incident on AM[C3H2O4]B(OH)3(H2O). x The crystal can produce green frequency-doubled light with a wavelength of 532nm, and the output intensity is about 0.5-1.2 times that of KDP under the same conditions.

Description

Technical Field

[0001] This invention relates to a series of malonate borate nonlinear optical crystals, their preparation methods, and applications. Background Technology

[0002] Ultraviolet nonlinear optical materials are key materials for generating coherent ultraviolet light in solid-state lasers. To obtain nonlinear optical materials with nonlinear optical properties, the commonly used international method is to introduce nonlinear optical functional units that easily cause distortion into the structure. These units mainly contain d... 0 d 10 Transition metal cation polyhedra or metal cation polyhedra containing lone pairs of electrons have electronic structures. However, these structural units often cause a redshift of the ultraviolet cutoff edge, making them unsuitable for use in the ultraviolet region. Borates, on the other hand, are characterized by their ability to transmit ultraviolet radiation. Many excellent nonlinear optical crystals have been discovered among borates, such as BBO (β-BBO), LBO (LiB3O5), CBO (CsB3O5), and CLBO (CsLiB6O5). 10 Nonlinear optical crystals include KBBF (KBe₂BO₃F₂) crystals. Although the crystal growth techniques for these materials have become increasingly mature, they still have significant drawbacks: such as hygroscopicity, long growth cycles, severe layered growth habits, and high cost. Therefore, synthesizing new nonlinear optical crystal materials remains a very important and challenging task. Summary of the Invention

[0003] The purpose of this invention is to provide a series of malonate borates AM[C3H2O4]B(OH)3(H2O). x Nonlinear optical crystal, where A = K, Rb, Cs, M = K, Rb, Cs, x = 0, 1, without a center of symmetry, orthorhombic crystal system, space group P212121 (No. 19), cell parameters: 1) K2[C3H2O4]B(OH)3: α=90, β=90, γ=90, Z=4, 2)KRb[C3H2O4]B(OH)3: a=6.6768(13) α=90, β=90, γ=90, Z=4, V=866.7(3) 3) KCs[C3H2O4]B(OH)3: α=90, β=90, γ=90, Z=4, 4) Rb2[C3H2O4]B(OH)3: α=90, β=90, γ=90, Z=4, 5) RbCs[C3H2O4]B(OH)3: α=90, β=90, γ=90, Z=4, 6) Cs2[C3H2O4]B(OH)3(H2O): α=90, β=90, γ=90, Z=4,

[0004] Another objective of this invention is to provide a method for preparing a series of malonate borate nonlinear optical crystals using a room temperature solution method.

[0005] Another object of the present invention is to provide a series of malonate borates AM[C3H2O4]B(OH)3(H2O) x Applications of nonlinear optical crystals.

[0006] The present invention relates to a series of malonate borate nonlinear optical crystals, the general molecular formula of which is AM[C3H2O4]B(OH)3(H2O). x Where A = K, Rb, Cs, M = K, Rb, Cs, x = 0, 1, no center of symmetry, orthorhombic crystal system, space group P212121, cell parameters: 1) K2[C3H2O4]B(OH)3: α=90, β=90, γ=90, Z=4, 2) KRb[C3H2O4]B(OH)3: α=90, β=90, γ=90, Z=4, 3) KCs[C3H2O4]B(OH)3: α=90, β=90, γ=90, Z=4, 4) Rb2[C3H2O4]B(OH)3: α=90, β=90, γ=90, Z=4, 5) RbCs[C3H2O4]B(OH)3: α=90, β=90, γ=90, Z=4, 6) Cs2[C3H2O4]B(OH)3(H2O): α=90, β=90, γ=90, Z=4,

[0007] The preparation method of the aforementioned series of malonate borate nonlinear optical crystals employs a room-temperature solution growth method, and the specific operation is carried out according to the following steps:

[0008] a. Mix the following compounds in a molar ratio of 1:1:0.5-2:0-1: C3H4O4 (containing malonic acid ester); H3BO3 (containing boron); K2CO3, Rb2CO3, Cs2CO3, KOH, RbOH, CsOH, KBF4, RbBF4 or CsBF4 (containing cation A); and K2CO3, Rb2CO3, Cs2CO3, KOH, RbOH, CsOH, KBF4, RbBF4 or CsBF4 (containing cation M) thoroughly. Add 30-50 mL of deionized water to fully mix and dissolve the mixture to obtain a solution.

[0009] b. The mixed solution from step a is ultrasonically treated to ensure thorough mixing and dissolution. Filter the solution using qualitative filter paper to obtain a clear solution. Seal the solution with a polyvinyl chloride film and place it in a static environment free from shaking, pollution, and air convection. Make several small holes in the seal to adjust the evaporation rate of the solvent in the solution. Let it stand at room temperature. Subsequently, crystals precipitate and gradually grow in the solution. Before the solvent has completely evaporated, remove the crystals and place them on filter paper to dry. This yields a series of nonlinear optical crystals of malonate borate, rubidium malonate borate, cesium malonate borate, rubidium malonate borate, rubidium malonate borate, or cesium malonate borate, with centimeter-sized crystals.

[0010] The use of the series of malonate borate nonlinear optical crystals in the fabrication of multi-band frequency doubling devices or optical elements.

[0011] The aforementioned series of malonate borate nonlinear optical crystals are used in the preparation of second- or third-harmonic output of the 1064nm fundamental frequency light from Nd:YAG lasers, with an output intensity approximately 0.5-1.2 times that of KDP under the same conditions.

[0012] The series of malonate borate nonlinear optical crystals are used in the fabrication of frequency multiplier generators, up or down frequency converters, or optical parametric oscillators.

[0013] The present invention discloses a method for preparing a series of malonate borate nonlinear optical crystals, through which a series of AM[C3H2O4]B(OH)3(H2O) crystals with centimeter-scale dimensions are obtained. x Nonlinear optical crystals do not exhibit a distinct layered growth habit. By using large-sized containers and extending the crystal growth period, correspondingly large-sized nonlinear optical crystals AM[C3H2O4]B(OH)3(H2O) can be obtained. x In this series AM[C3H2O4]B(OH)3(H2O) xNonlinear optical crystals are easy to grow into transparent, unencapsulated crystals, and have advantages such as fast growth rate, low cost, and easy acquisition of large-size crystals.

[0014] Using the method described in this invention, a large-size series AM[C3H2O4]B(OH)3(H2O) is obtained. x Nonlinear optical crystals are produced by orienting the crystal blank according to its crystallographic data, cutting the crystal to the required angle, thickness, and cross-sectional dimensions, and polishing the light-transmitting surface of the crystal. This allows it to be used as a nonlinear optical device. This series includes AM[C3H2O4]B(OH)3(H2O). x Nonlinear optical crystals have advantages such as a wide transmission band, stable physicochemical properties, moderate mechanical hardness, resistance to breakage, and ease of cutting, polishing, and storage. Attached Figure Description

[0015] Figure 1 The compound of this invention is AM[C3H2O4]B(OH)3(H2O). x Powder XRD patterns of (A=K, Rb, Cs, M=K, Rb, Cs, x=0, 1);

[0016] Figure 2 The present invention is AM[C3H2O4]B(OH)3(H2O). x (A = K, Rb, Cs, M = K, Rb, Cs, x = 0, 1) Crystal structure diagram.

[0017] Figure 3 The present invention is AM[C3H2O4]B(OH)3(H2O). x (A=K, Rb, Cs, M=K, Rb, Cs, x=0, 1) Schematic diagram of the working principle of a nonlinear optical device made of crystal, where 1 is the laser, 2 is the emitted beam, and 3 is AM[C3H2O4]B(OH)3(H2O). x (A = K, Rb, Cs, M = K, Rb, Cs, x = 0, 1) Crystal, 4 is the emitted beam, 5 is the filter; Detailed Implementation

[0018] The present invention will now be described in detail with reference to the accompanying drawings and embodiments:

[0019] Example 1

[0020] According to the reaction formula: C3H4O4 + H3BO3 + K2CO3 → K2[C3H2O4]B(OH)3 + CO2↑ + H2O↑, the K2[C3H2O4]B(OH)3 nonlinear optical crystal was prepared by room temperature solution method.

[0021] a. Mix C3H4O4, H3BO3 and K2CO3 evenly in a molar ratio of 1:1:1, add 50mL of deionized water to mix and dissolve thoroughly to obtain a mixed solution;

[0022] b. The mixed solution from step a is sonicated to ensure thorough mixing and dissolution. It is then filtered through qualitative filter paper to obtain a clear solution. The solution is then sealed with a polyvinyl chloride film and placed in a static environment free from shaking, contamination, and air convection. Several small holes are punched in the seal to adjust the evaporation rate of the solvent in the solution. The solution is left to stand at room temperature. Subsequently, crystals precipitate out of the solution and gradually grow. Before the solvent has completely evaporated, the crystals are removed. The product in the polytetrafluoroethylene beaker is quickly washed with deionized water and placed on filter paper to dry. This yields a K2[C3H2O4]B(OH)3 nonlinear optical crystal with dimensions of 18mm×18mm×8mm.

[0023] Example 2

[0024] According to the reaction formula: C3H4O4 + H3BO3 + 0.5K2CO3 + 0.5Rb2CO3 → KRb[C3H2O4]B(OH)3 + CO2↑ + H2O↑, KRb[C3H2O4]B(OH)3 nonlinear optical crystals were prepared by room temperature solution method.

[0025] a. Mix C3H4O4, H3BO3, K2CO3 and Rb2CO3 evenly in a molar ratio of 1:1:0.5:0.5, add 50mL of deionized water to mix and dissolve thoroughly to obtain a mixed solution;

[0026] b. The mixed solution from step a is ultrasonically treated to ensure thorough mixing and dissolution. It is then filtered with qualitative filter paper to obtain a clear solution. The solution is then sealed with a polyvinyl chloride film and placed in a static environment free from shaking, pollution, and air convection. Several small holes are punched in the seal to adjust the evaporation rate of the solvent in the solution. The solution is left to stand at room temperature. Subsequently, crystals precipitate out of the solution and gradually grow. Before the solvent has completely evaporated, the crystals are removed. The product in the polytetrafluoroethylene beaker is quickly washed with deionized water and placed on filter paper to dry. This yields a KRb[C3H2O4]B(OH)3 nonlinear optical crystal with dimensions of 18mm×17mm×10mm.

[0027] Example 3

[0028] Based on the reaction formula: C3H4O4 + H3BO3 + 0.5K2CO3 + 0.5Cs2CO3 → KCs[C3H2O4]B(OH)3 + CO2↑ + H2O↑, KCs[C3H2O4]B(OH)3 nonlinear optical crystals were prepared using a room temperature solution method.

[0029] a. Mix C3H4O4, H3BO3, K2CO3 and Cs2CO3 evenly in a molar ratio of 1:1:0.5:0.5, add 50mL of deionized water to mix and dissolve thoroughly to obtain a mixed solution;

[0030] b. The mixed solution from step a is ultrasonically treated to ensure thorough mixing and dissolution. It is then filtered with qualitative filter paper to obtain a clear solution. The solution is then sealed with a polyvinyl chloride film and placed in a static environment free from shaking, pollution, and air convection. Several small holes are punched in the seal to adjust the evaporation rate of the solvent in the solution. The solution is left to stand at room temperature. Subsequently, crystals precipitate out of the solution and gradually grow. Before the solvent has completely evaporated, the crystals are removed. The product in the polytetrafluoroethylene beaker is quickly washed with deionized water and placed on filter paper to dry. This yields a KCs[C3H2O4]B(OH)3 nonlinear optical crystal with dimensions of 21mm×16mm×11mm.

[0031] Example 4

[0032] Based on the reaction formula: C3H4O4 + H3BO3 + Rb2CO3 → Rb2[C3H2O4]B(OH)3 + CO2↑ + H2O↑, the nonlinear optical crystal Rb2[C3H2O4]B(OH)3 was prepared by a room temperature solution method.

[0033] a. Mix C3H4O4, H3BO3, and Rb2CO3 in a molar ratio of 1:1:1 until homogeneous, then add 50 mL of deionized water and mix thoroughly to obtain a mixed solution.

[0034] b. The mixed solution from step a is ultrasonically treated to ensure thorough mixing and dissolution. It is then filtered with qualitative filter paper to obtain a clear solution. The solution is then sealed with a polyvinyl chloride film and placed in a static environment free from shaking, pollution, and air convection. Several small holes are punched in the seal to adjust the evaporation rate of the solvent in the solution. The solution is left to stand at room temperature. Subsequently, crystals precipitate out of the solution and gradually grow. Before the solvent has completely evaporated, the crystals are removed. The product in the polytetrafluoroethylene beaker is quickly washed with deionized water and placed on filter paper to dry. This yields a Rb2[C3H2O4]B(OH)3 nonlinear optical crystal with dimensions of 19mm×14mm×7mm.

[0035] Example 5

[0036] Based on the reaction formula: C3H4O4 + H3BO3 + 0.5Rb2CO3 + 0.5Cs2CO3 → RbCs[C3H2O4]B(OH)3 + CO2↑ + H2O↑, the RbCs[C3H2O4]B(OH)3 nonlinear optical crystal was prepared by room temperature solution method.

[0037] a. Mix C3H4O4, H3BO3, Rb2CO3, and Cs2CO3 thoroughly in a molar ratio of 1:1:0.5:0.5, then add 50 mL of deionized water to fully dissolve and mix, obtaining a mixed solution.

[0038] b. The mixed solution from step a is ultrasonically treated to ensure thorough mixing and dissolution. It is then filtered with qualitative filter paper to obtain a clear solution. The solution is then sealed with a polyvinyl chloride film and placed in a static environment free from shaking, pollution, and air convection. Several small holes are punched in the seal to adjust the evaporation rate of the solvent in the solution. The solution is left to stand at room temperature. Subsequently, crystals precipitate out and gradually grow in the solution. Before the solvent has completely evaporated, the crystals are removed. The product in the polytetrafluoroethylene beaker is quickly washed with deionized water and placed on filter paper to dry. This yields a RbCs[C3H2O4]B(OH)3 nonlinear optical crystal with dimensions of 18mm×11mm×6mm.

[0039] Example 6

[0040] According to the reaction formula: C3H4O4 + H3BO3 + Cs2CO3 → Cs2[C3H2O4]B(OH)3(H2O) + CO2↑, the nonlinear optical crystal Cs2[C3H2O4]B(OH)3(H2O) was prepared by a room temperature solution method.

[0041] a. Mix C3H4O4, H3BO3, and Cs2CO3 in a molar ratio of 1:1:1 until homogeneous, then add 50 mL of deionized water and mix thoroughly to obtain a mixed solution.

[0042] b. The mixed solution from step a is ultrasonically treated to ensure thorough mixing and dissolution. It is then filtered with qualitative filter paper to obtain a clear solution. The solution is then sealed with a polyvinyl chloride film and placed in a static environment free from shaking, pollution, and air convection. Several small holes are punched in the seal to adjust the evaporation rate of the solvent in the solution. The solution is left to stand at room temperature. Subsequently, crystals precipitate out of the solution and gradually grow. Before the solvent has completely evaporated, the crystals are removed. The product in the polytetrafluoroethylene beaker is quickly washed with deionized water and placed on filter paper to dry. This yields a Cs2[C3H2O4]B(OH)3(H2O) nonlinear optical crystal with dimensions of 16mm×14mm×7mm.

[0043] Example 7

[0044] Based on the reaction formula: C3H4O4 + H3BO3 + 0.5K2CO3 + KOH → K2[C3H2O4]B(OH)3 + 0.5CO2↑ + 1.5H2O↑, the K2[C3H2O4]B(OH)3 nonlinear optical crystal was prepared by room temperature solution method.

[0045] a. Mix C3H4O4, H3BO3, K2CO3, and KOH in a molar ratio of 1:1:0.5:1 until homogeneous. Add 40 mL of deionized water and mix thoroughly to obtain a mixed solution.

[0046] b. The mixed solution from step a is ultrasonically treated to ensure thorough mixing and dissolution. It is then filtered with qualitative filter paper to obtain a clear solution. The solution is then sealed with a polyvinyl chloride film and placed in a static environment free from shaking, pollution, and air convection. Several small holes are punched in the seal to adjust the evaporation rate of the solvent in the solution. The solution is left to stand at room temperature. Subsequently, crystals precipitate out of the solution and gradually grow. Before the solvent has completely evaporated, the crystals are removed. The product in the polytetrafluoroethylene beaker is quickly washed with deionized water and placed on filter paper to dry. This yields a K2[C3H2O4]B(OH)3 nonlinear optical crystal with dimensions of 14mm×13mm×9mm.

[0047] Example 8

[0048] Based on the reaction formula: C3H4O4 + H3BO3 + 0.5Rb2CO3 + RbOH → Rb2[C3H2O4]B(OH)3 + 0.5CO2↑ + 1.5H2O↑, the Rb2[C3H2O4]B(OH)3 nonlinear optical crystal was prepared by room temperature solution method.

[0049] a. Mix C3H4O4, H3BO3, Rb2CO3, and RbOH in a molar ratio of 1:1:0.5:1 until homogeneous. Add 40 mL of deionized water and mix thoroughly to obtain a mixed solution.

[0050] b. The mixed solution from step a is ultrasonically treated to ensure thorough mixing and dissolution. It is then filtered with qualitative filter paper to obtain a clear solution. The solution is then sealed with a polyvinyl chloride film and placed in a static environment free from shaking, contamination, and air convection. Several small holes are punched in the seal to adjust the evaporation rate of the solvent in the solution. The solution is left to stand at room temperature. Subsequently, crystals precipitate out of the solution and gradually grow. Before the solvent has completely evaporated, the crystals are removed. The product in the polytetrafluoroethylene beaker is quickly washed with deionized water and placed on filter paper to dry. This yields a Rb2[C3H2O4]B(OH)3 nonlinear optical crystal with dimensions of 18mm×16mm×8mm.

[0051] Example 9

[0052] Based on the reaction formula: C3H4O4 + H3BO3 + 0.5Cs2CO3 + CsOH → Cs2[C3H2O4]B(OH)3(H2O) + 0.5CO2↑ + 0.5H2O↑, the Cs2[C3H2O4]B(OH)3(H2O) nonlinear optical crystal was prepared by room temperature solution method.

[0053] a. Mix C3H4O4, H3BO3, Cs2CO3, and CsOH evenly in a molar ratio of 1:1:0.5:1, add 40mL of deionized water to fully mix and dissolve, and obtain a mixed solution;

[0054] b. The mixed solution from step a is ultrasonically treated to ensure thorough mixing and dissolution. It is then filtered with qualitative filter paper to obtain a clear solution. The solution is then sealed with a polyvinyl chloride film and placed in a static environment free from shaking, pollution, and air convection. Several small holes are punched in the seal to adjust the evaporation rate of the solvent in the solution. The solution is left to stand at room temperature. Subsequently, crystals precipitate out of the solution and gradually grow. Before the solvent has completely evaporated, the crystals are removed. The product in the polytetrafluoroethylene beaker is quickly washed with deionized water and placed on filter paper to dry. This yields a Cs2[C3H2O4]B(OH)3(H2O) nonlinear optical crystal with dimensions of 18mm×16mm×9mm.

[0055] Example 10

[0056] According to the reaction formula: C3H4O4 + H3BO3 + 2KOH → K2[C3H2O4]B(OH)3 + 2H2O↑, the K2[C3H2O4]B(OH)3 nonlinear optical crystal was prepared by room temperature solution method.

[0057] a. Mix C3H4O4, H3BO3 and KOH evenly in a molar ratio of 1:1:2, add 30mL of deionized water to mix and dissolve thoroughly to obtain a mixed solution;

[0058] b. The mixed solution from step a is ultrasonically treated to ensure thorough mixing and dissolution. It is then filtered with qualitative filter paper to obtain a clear solution. The solution is then sealed with a polyvinyl chloride film and placed in a static environment free from shaking, pollution, and air convection. Several small holes are punched in the seal to adjust the evaporation rate of the solvent in the solution. The solution is left to stand at room temperature. Subsequently, crystals precipitate out of the solution and gradually grow. Before the solvent has completely evaporated, the crystals are removed. The product in the polytetrafluoroethylene beaker is quickly washed with deionized water and placed on filter paper to dry. This yields a K2[C3H2O4]B(OH)3 nonlinear optical crystal with dimensions of 19mm×17mm×7mm.

[0059] Example 11

[0060] According to the reaction formula: C3H4O4 + H3BO3 + KOH + RbOH → KRb[C3H2O4]B(OH)3 + 2H2O↑, KRb[C3H2O4]B(OH)3 nonlinear optical crystals were prepared by room temperature solution method.

[0061] a. Mix C3H4O4, H3BO3, KOH, and RbOH evenly in a molar ratio of 1:1:1:1, add 30mL of deionized water to fully mix and dissolve, and obtain a mixed solution;

[0062] b. The mixed solution from step a is ultrasonically treated to ensure thorough mixing and dissolution. It is then filtered with qualitative filter paper to obtain a clear solution. The solution is then sealed with a polyvinyl chloride film and placed in a static environment free from shaking, pollution, and air convection. Several small holes are punched in the seal to adjust the evaporation rate of the solvent in the solution. The solution is left to stand at room temperature. Subsequently, crystals precipitate out of the solution and gradually grow. Before the solvent has completely evaporated, the crystals are removed. The product in the polytetrafluoroethylene beaker is quickly washed with deionized water and placed on filter paper to dry. This yields a KRb[C3H2O4]B(OH)3 nonlinear optical crystal with dimensions of 17mm×14mm×6mm.

[0063] Example 12

[0064] According to the reaction formula: C3H4O4 + H3BO3 + KOH + CsOH → KCs[C3H2O4]B(OH)3 + 2H2O↑, the nonlinear optical crystal KCs[C3H2O4]B(OH)3 was prepared by a room temperature solution method.

[0065] a. Mix C3H4O4, H3BO3, KOH, and CsOH evenly in a molar ratio of 1:1:1:1, add 30 mL of deionized water to fully mix and dissolve, and obtain a mixed solution;

[0066] b. The mixed solution from step a is ultrasonically treated to ensure thorough mixing and dissolution. It is then filtered with qualitative filter paper to obtain a clear solution. The solution is then sealed with a polyvinyl chloride film and placed in a static environment free from shaking, pollution, and air convection. Several small holes are punched in the seal to adjust the evaporation rate of the solvent in the solution. The solution is left to stand at room temperature. Subsequently, crystals precipitate out of the solution and gradually grow. Before the solvent has completely evaporated, the crystals are removed. The product in the polytetrafluoroethylene beaker is quickly washed with deionized water and placed on filter paper to dry. This yields a KCs[C3H2O4]B(OH)3 nonlinear optical crystal with dimensions of 20mm×12mm×6mm.

[0067] Example 13

[0068] According to the reaction formula: C3H4O4 + H3BO3 + 2RbOH → Rb2[C3H2O4]B(OH)3 + 2H2O↑, the nonlinear optical crystal Rb2[C3H2O4]B(OH)3 was prepared by room temperature solution method.

[0069] a. Mix C3H4O4, H3BO3 and RbOH evenly in a molar ratio of 1:1:2, add 30mL of deionized water to mix and dissolve thoroughly to obtain a mixed solution;

[0070] b. The mixed solution from step a is ultrasonically treated to ensure thorough mixing and dissolution. It is then filtered with qualitative filter paper to obtain a clear solution. The solution is then sealed with a polyvinyl chloride film and placed in a static environment free from shaking, pollution, and air convection. Several small holes are punched in the seal to adjust the evaporation rate of the solvent in the solution. The solution is left to stand at room temperature. Subsequently, crystals precipitate out of the solution and gradually grow. Before the solvent has completely evaporated, the crystals are removed. The product in the polytetrafluoroethylene beaker is quickly washed with deionized water and placed on filter paper to dry. This yields a Rb2[C3H2O4]B(OH)3 nonlinear optical crystal with dimensions of 21mm×15mm×8mm.

[0071] Example 14

[0072] According to the reaction formula: C3H4O4 + H3BO3 + RbOH + CsOH → RbCs[C3H2O4]B(OH)3 + 2H2O↑, the nonlinear optical crystal RbCs[C3H2O4]B(OH)3 was prepared by room temperature solution method.

[0073] a. Mix C3H4O4, H3BO3, RbOH, and CsOH evenly in a molar ratio of 1:1:1:1, add 30mL of deionized water to fully mix and dissolve, and obtain a mixed solution;

[0074] b. The mixed solution from step a is ultrasonically treated to ensure thorough mixing and dissolution. It is then filtered with qualitative filter paper to obtain a clear solution. The solution is then sealed with a polyvinyl chloride film and placed in a static environment free from shaking, contamination, and air convection. Several small holes are punched in the seal to adjust the evaporation rate of the solvent in the solution. The solution is left to stand at room temperature. Subsequently, crystals precipitate out of the solution and gradually grow. Before the solvent has completely evaporated, the crystals are removed. The product in the polytetrafluoroethylene beaker is quickly washed with deionized water and placed on filter paper to dry, thus obtaining a RbCs[C3H2O4]B(OH)3 nonlinear optical crystal with dimensions of 17mm×15mm×6mm.

[0075] Example 15

[0076] According to the reaction formula: C3H4O4 + H3BO3 + 2CsOH → Cs2[C3H2O4]B(OH)3(H2O) + H2O↑, the nonlinear optical crystal Cs2[C3H2O4]B(OH)3(H2O) was prepared by a room temperature solution method.

[0077] a. Mix C3H4O4, H3BO3, and CsOH in a molar ratio of 1:1:2 until homogeneous, add 30mL of deionized water and mix thoroughly to obtain a mixed solution;

[0078] b. The mixed solution from step a is ultrasonically treated to ensure thorough mixing and dissolution. It is then filtered with qualitative filter paper to obtain a clear solution. The solution is then sealed with a polyvinyl chloride film and placed in a static environment free from shaking, pollution, and air convection. Several small holes are punched in the seal to adjust the evaporation rate of the solvent in the solution. The solution is left to stand at room temperature. Subsequently, crystals precipitate out of the solution and gradually grow. Before the solvent has completely evaporated, the crystals are removed. The product in the polytetrafluoroethylene beaker is quickly washed with deionized water and placed on filter paper to dry. This yields a Cs2[C3H2O4]B(OH)3(H2O) nonlinear optical crystal with dimensions of 17mm×12mm×7mm.

[0079] Example 16

[0080] According to the reaction formula: C3H4O4 + H3BO3 + 0.5K2CO3 + RbOH → KRb[C3H2O4]B(OH)3 + 0.5CO2↑ + 1.5H2O↑, KRb[C3H2O4]B(OH)3 nonlinear optical crystal was prepared by room temperature solution method.

[0081] a. Mix C3H4O4, H3BO3, K2CO3, and RbOH evenly in a molar ratio of 1:1:0.5:1, add 40mL of deionized water to fully mix and dissolve, and obtain a mixed solution;

[0082] b. The mixed solution from step a is ultrasonically treated to ensure thorough mixing and dissolution. It is then filtered with qualitative filter paper to obtain a clear solution. The solution is then sealed with a polyvinyl chloride film and placed in a static environment free from shaking, pollution, and air convection. Several small holes are punched in the seal to adjust the evaporation rate of the solvent in the solution. The solution is left to stand at room temperature. Subsequently, crystals precipitate out of the solution and gradually grow. Before the solvent has completely evaporated, the crystals are removed. The product in the polytetrafluoroethylene beaker is quickly washed with deionized water and placed on filter paper to dry. This yields a KRb[C3H2O4]B(OH)3 nonlinear optical crystal with dimensions of 22mm×16mm×10mm.

[0083] Example 17

[0084] According to the reaction formula: C3H4O4 + H3BO3 + 0.5Rb2CO3 + KOH → KRb[C3H2O4]B(OH)3 + 0.5CO2↑ + 1.5H2O↑, KRb[C3H2O4]B(OH)3 nonlinear optical crystal was prepared by room temperature solution method.

[0085] a. Mix C3H4O4, H3BO3, Rb2CO3, and KOH evenly in a molar ratio of 1:1:0.5:1, add 40mL of deionized water to fully mix and dissolve, and obtain a mixed solution;

[0086] b. The mixed solution from step a is ultrasonically treated to ensure thorough mixing and dissolution. It is then filtered with qualitative filter paper to obtain a clear solution. The solution is then sealed with a polyvinyl chloride film and placed in a static environment free from shaking, pollution, and air convection. Several small holes are punched in the seal to adjust the evaporation rate of the solvent in the solution. The solution is left to stand at room temperature. Subsequently, crystals precipitate out of the solution and gradually grow. Before the solvent has completely evaporated, the crystals are removed. The product in the polytetrafluoroethylene beaker is quickly washed with deionized water and placed on filter paper to dry, thus obtaining a KRb[C3H2O4]B(OH)3 nonlinear optical crystal with dimensions of 20mm×15mm×10mm.

[0087] Example 18

[0088] According to the reaction formula: C3H4O4 + H3BO3 + 0.5K2CO3 + CsOH → KCs[C3H2O4]B(OH)3 + 0.5CO2↑ + 1.5H2O↑, the KCs[C3H2O4]B(OH)3 nonlinear optical crystal was prepared by room temperature solution method.

[0089] a. Mix C3H4O4, H3BO3, K2CO3, and CsOH evenly in a molar ratio of 1:1:0.5:1, add 40mL of deionized water to fully mix and dissolve, and obtain a mixed solution;

[0090] b. The mixed solution from step a is ultrasonically treated to ensure thorough mixing and dissolution. It is then filtered with qualitative filter paper to obtain a clear solution. The solution is then sealed with a polyvinyl chloride film and placed in a static environment free from shaking, pollution, and air convection. Several small holes are punched in the seal to adjust the evaporation rate of the solvent in the solution. The solution is left to stand at room temperature. Subsequently, crystals precipitate out of the solution and gradually grow. Before the solvent has completely evaporated, the crystals are removed. The product in the polytetrafluoroethylene beaker is quickly washed with deionized water and placed on filter paper to dry. This yields a KCs[C3H2O4]B(OH)3 nonlinear optical crystal with dimensions of 22mm×16mm×10mm.

[0091] Example 19

[0092] According to the reaction formula: C3H4O4 + H3BO3 + 0.5Cs2CO3 + KOH → KCs[C3H2O4]B(OH)3 + 0.5CO2↑ + 1.5H2O↑, KCs[C3H2O4]B(OH)3 nonlinear optical crystal was prepared by room temperature solution method.

[0093] a. Mix C3H4O4, H3BO3, Cs2CO3 and KOH evenly in a molar ratio of 1:1:0.5:1, add 40mL of deionized water to mix and dissolve thoroughly to obtain a mixed solution;

[0094] b. The mixed solution from step a is ultrasonically treated to ensure thorough mixing and dissolution. It is then filtered with qualitative filter paper to obtain a clear solution. The solution is then sealed with a polyvinyl chloride film and placed in a static environment free from shaking, pollution, and air convection. Several small holes are punched in the seal to adjust the evaporation rate of the solvent in the solution. The solution is left to stand at room temperature. Subsequently, crystals precipitate out of the solution and gradually grow. Before the solvent has completely evaporated, the crystals are removed. The product in the polytetrafluoroethylene beaker is quickly washed with deionized water and placed on filter paper to dry. This yields a KCs[C3H2O4]B(OH)3 nonlinear optical crystal with dimensions of 19mm×17mm×10mm.

[0095] Example 20

[0096] Based on the reaction formula: C3H4O4 + H3BO3 + 0.5Rb2CO3 + CsOH → RbCs[C3H2O4]B(OH)3 + 0.5CO2↑ + 1.5H2O↑, the RbCs[C3H2O4]B(OH)3 nonlinear optical crystal was prepared by room temperature solution method.

[0097] a. Mix C3H4O4, H3BO3, Rb2CO3, and CsOH evenly in a molar ratio of 1:1:0.5:1, add 40mL of deionized water to fully mix and dissolve, and obtain a mixed solution;

[0098] b. The mixed solution from step a is ultrasonically treated to ensure thorough mixing and dissolution. It is then filtered with qualitative filter paper to obtain a clear solution. The solution is then sealed with a polyvinyl chloride film and placed in a static environment free from shaking, pollution, and air convection. Several small holes are punched in the seal to adjust the evaporation rate of the solvent in the solution. The solution is left to stand at room temperature. Subsequently, crystals precipitate out of the solution and gradually grow. Before the solvent has completely evaporated, the crystals are removed. The product in the polytetrafluoroethylene beaker is quickly washed with deionized water and placed on filter paper to dry. This yields a RbCs[C3H2O4]B(OH)3 nonlinear optical crystal with dimensions of 18mm×17mm×10mm.

[0099] Example 21

[0100] Based on the reaction formula: C3H4O4 + H3BO3 + 0.5Cs2CO3 + RbOH → RbCs[C3H2O4]B(OH)3 + 0.5CO2↑ + 1.5H2O↑, the RbCs[C3H2O4]B(OH)3 nonlinear optical crystal was prepared by room temperature solution method.

[0101] a. Mix C3H4O4, H3BO3, Cs2CO3 and RbOH evenly in a molar ratio of 1:1:0.5:1, add 40mL of deionized water to mix and dissolve thoroughly to obtain a mixed solution;

[0102] b. The mixed solution from step a is ultrasonically treated to ensure thorough mixing and dissolution. It is then filtered with qualitative filter paper to obtain a clear solution. The solution is then sealed with a polyvinyl chloride film and placed in a static environment free from shaking, pollution, and air convection. Several small holes are punched in the seal to adjust the evaporation rate of the solvent in the solution. The solution is left to stand at room temperature. Subsequently, crystals precipitate out of the solution and gradually grow. Before the solvent has completely evaporated, the crystals are removed. The product in the polytetrafluoroethylene beaker is quickly washed with deionized water and placed on filter paper to dry, thus obtaining a RbCs[C3H2O4]B(OH)3 nonlinear optical crystal with dimensions of 19mm×16mm×9mm.

[0103] Example 22

[0104] According to the reaction formula: C3H4O4 + H3BO3 + 2KBF4 → K2[C3H2O4]B(OH)3 + 2HBF4, the K2[C3H2O4]B(OH)3 nonlinear optical crystal was prepared by room temperature solution method.

[0105] a. Mix C3H4O4, H3BO3, and KBF4 evenly in a molar ratio of 1:1:2, add 50mL of deionized water to fully mix and dissolve them to obtain a mixed solution;

[0106] b. The mixed solution from step a is ultrasonically treated to ensure thorough mixing and dissolution. It is then filtered with qualitative filter paper to obtain a clear solution. The solution is then sealed with a polyvinyl chloride film and placed in a static environment free from shaking, pollution, and air convection. Several small holes are punched in the seal to adjust the evaporation rate of the solvent in the solution. The solution is left to stand at room temperature. Subsequently, crystals precipitate out of the solution and gradually grow. Before the solvent has completely evaporated, the crystals are removed. The product in the polytetrafluoroethylene beaker is quickly washed with deionized water and placed on filter paper to dry. This yields a K2[C3H2O4]B(OH)3 nonlinear optical crystal with dimensions of 22mm×18mm×10mm.

[0107] Example 23

[0108] According to the reaction formula: C3H4O4 + H3BO3 + 2RbBF4 → Rb2[C3H2O4]B(OH)3 + 2HBF4, the nonlinear optical crystal Rb2[C3H2O4]B(OH)3 was prepared by room temperature solution method.

[0109] a. Mix C3H4O4, H3BO3, and RbBF4 evenly in a molar ratio of 1:1:2, add 50mL of deionized water to fully mix and dissolve, and obtain a mixed solution;

[0110] b. The mixed solution from step a is ultrasonically treated to ensure thorough mixing and dissolution. It is then filtered with qualitative filter paper to obtain a clear solution. The solution is then sealed with a polyvinyl chloride film and placed in a static environment free from shaking, contamination, and air convection. Several small holes are punched in the seal to adjust the evaporation rate of the solvent in the solution. The solution is left to stand at room temperature. Subsequently, crystals precipitate out of the solution and gradually grow. Before the solvent has completely evaporated, the crystals are removed. The product in the polytetrafluoroethylene beaker is quickly washed with deionized water and placed on filter paper to dry. This yields a Rb2[C3H2O4]B(OH)3 nonlinear optical crystal with dimensions of 20mm×15mm×9mm.

[0111] Example 24

[0112] Based on the reaction formula: C3H4O4 + H3BO3 + 2CsBF4 + H2O → Cs2[C3H2O4]B(OH)3(H2O) + 2HBF4, the Cs2[C3H2O4]B(OH)3(H2O) nonlinear optical crystal was prepared by room temperature solution method.

[0113] a. Mix C3H4O4, H3BO3, and CsBF4 evenly in a molar ratio of 1:1:2, add 50mL of deionized water to fully mix and dissolve, and obtain a mixed solution;

[0114] b. The mixed solution from step a is ultrasonically treated to ensure thorough mixing and dissolution. It is then filtered with qualitative filter paper to obtain a clear solution. The solution is then sealed with a polyvinyl chloride film and placed in a static environment free from shaking, pollution, and air convection. Several small holes are punched in the seal to adjust the evaporation rate of the solvent in the solution. The solution is left to stand at room temperature. Subsequently, crystals precipitate out of the solution and gradually grow. Before the solvent has completely evaporated, the crystals are removed. The product in the polytetrafluoroethylene beaker is quickly washed with deionized water and placed on filter paper to dry. This yields a Cs2[C3H2O4]B(OH)3(H2O) nonlinear optical crystal with dimensions of 16mm×13mm×8mm.

[0115] Example 25

[0116] According to the reaction formula: C3H4O4 + H3BO3 + KBF4 + RbKBF4 → KRb[C3H2O4]B(OH)3 + 2HBF4, KRb[C3H2O4]B(OH)3 nonlinear optical crystal was prepared by room temperature solution method.

[0117] a. Mix C3H4O4, H3BO3, KBF4, and RbBF4 evenly in a molar ratio of 1:1:1:1, add 50mL of deionized water to fully mix and dissolve, and obtain a mixed solution;

[0118] b. The mixed solution from step a is ultrasonically treated to ensure thorough mixing and dissolution. It is then filtered with qualitative filter paper to obtain a clear solution. The solution is then sealed with a polyvinyl chloride film and placed in a static environment free from shaking, contamination, and air convection. Several small holes are punched in the seal to adjust the evaporation rate of the solvent in the solution. The solution is left to stand at room temperature. Subsequently, crystals precipitate out of the solution and gradually grow. Before the solvent has completely evaporated, the crystals are removed. The product in the polytetrafluoroethylene beaker is quickly washed with deionized water and placed on filter paper to dry. This yields a KRb[C3H2O4]B(OH)3 nonlinear optical crystal with dimensions of 19mm×18mm×10mm.

[0119] Example 26

[0120] According to the reaction formula: C3H4O4 + H3BO3 + KBF4 + CsKBF4 → KCs[C3H2O4]B(OH)3 + 2HBF4, the nonlinear optical crystal KCs[C3H2O4]B(OH)3 was prepared by a room temperature solution method.

[0121] a. Mix C3H4O4, H3BO3, KBF4, and CsBF4 evenly in a molar ratio of 1:1:1:1, add 50mL of deionized water to fully mix and dissolve, and obtain a mixed solution;

[0122] b. The mixed solution from step a is ultrasonically treated to ensure thorough mixing and dissolution. It is then filtered with qualitative filter paper to obtain a clear solution. The solution is then sealed with a polyvinyl chloride film and placed in a static environment free from shaking, pollution, and air convection. Several small holes are punched in the seal to adjust the evaporation rate of the solvent in the solution. The solution is left to stand at room temperature. Subsequently, crystals precipitate out of the solution and gradually grow. Before the solvent has completely evaporated, the crystals are removed. The product in the polytetrafluoroethylene beaker is quickly washed with deionized water and placed on filter paper to dry. This yields a KCs[C3H2O4]B(OH)3 nonlinear optical crystal with dimensions of 21mm×19mm×10mm.

[0123] Example 27

[0124] According to the reaction formula: C3H4O4 + H3BO3 + RbBF4 + CsKBF4 → RbCs[C3H2O4]B(OH)3 + 2HBF4, the nonlinear optical crystal RbCs[C3H2O4]B(OH)3 was prepared by room temperature solution method.

[0125] a. Mix C3H4O4, H3BO3, RbBF4 and CsBF4 evenly in a molar ratio of 1:1:1:1, add 50mL of deionized water to mix and dissolve thoroughly to obtain a mixed solution;

[0126] b. The mixed solution from step a is ultrasonically treated to ensure thorough mixing and dissolution. It is then filtered with qualitative filter paper to obtain a clear solution. The solution is then sealed with a polyvinyl chloride film and placed in a static environment free from shaking, pollution, and air convection. Several small holes are punched in the seal to adjust the evaporation rate of the solvent in the solution. The solution is left to stand at room temperature. Subsequently, crystals precipitate out of the solution and gradually grow. Before the solvent has completely evaporated, the crystals are removed. The product in the polytetrafluoroethylene beaker is quickly washed with deionized water and placed on filter paper to dry. This yields a RbCs[C3H2O4]B(OH)3 nonlinear optical crystal with dimensions of 20mm×16mm×8mm.

[0127] Example 28

[0128] According to the reaction formula: C3H4O4 + H3BO3 + KBF4 + KOH → K2[C3H2O4]B(OH)3 + HBF4 + H2O↑, the K2[C3H2O4]B(OH)3 nonlinear optical crystal was prepared by room temperature solution method.

[0129] a. Mix C3H4O4, H3BO3, KBF4, and KOH evenly in a molar ratio of 1:1:1:1, add 50mL of deionized water to fully mix and dissolve, and obtain a mixed solution;

[0130] b. The mixed solution from step a is ultrasonically treated to ensure thorough mixing and dissolution. It is then filtered with qualitative filter paper to obtain a clear solution. The solution is then sealed with a polyvinyl chloride film and placed in a static environment free from shaking, pollution, and air convection. Several small holes are punched in the seal to adjust the evaporation rate of the solvent in the solution. The solution is left to stand at room temperature. Subsequently, crystals precipitate out of the solution and gradually grow. Before the solvent has completely evaporated, the crystals are removed. The product in the polytetrafluoroethylene beaker is quickly washed with deionized water and placed on filter paper to dry. This yields a K2[C3H2O4]B(OH)3 nonlinear optical crystal with dimensions of 19mm×15mm×7mm.

[0131] Example 29

[0132] According to the reaction formula: C3H4O4 + H3BO3 + RbBF4 + RbOH → Rb2[C3H2O4]B(OH)3 + HBF4 + H2O↑, the nonlinear optical crystal Rb2[C3H2O4]B(OH)3 was prepared by room temperature solution method.

[0133] a. Mix C3H4O4, H3BO3, RbBF4, and RbOH in a molar ratio of 1:1:1:1, add 50 mL of deionized water to fully mix and dissolve, and obtain a mixed solution;

[0134] b. The mixed solution from step a is ultrasonically treated to ensure thorough mixing and dissolution. It is then filtered with qualitative filter paper to obtain a clear solution. The solution is then sealed with a polyvinyl chloride film and placed in a static environment free from shaking, pollution, and air convection. Several small holes are punched in the seal to adjust the evaporation rate of the solvent in the solution. The solution is left to stand at room temperature. Subsequently, crystals precipitate out of the solution and gradually grow. Before the solvent has completely evaporated, the crystals are removed. The product in the polytetrafluoroethylene beaker is quickly washed with deionized water and placed on filter paper to dry. This yields a Rb2[C3H2O4]B(OH)3 nonlinear optical crystal with dimensions of 20mm×16mm×8mm.

[0135] Example 30

[0136] Based on the reaction formula: C3H4O4 + H3BO3 + CsBF4 + CsOH → Cs2[C3H2O4]B(OH)3(H2O) + HBF4, the Cs2[C3H2O4]B(OH)3(H2O) nonlinear optical crystal was prepared by room temperature solution method.

[0137] a. Mix C3H4O4, H3BO3, CsBF4, and CsOH in a molar ratio of 1:1:1:1, add 50 mL of deionized water to fully mix and dissolve, and obtain a mixed solution;

[0138] b. The mixed solution from step a is ultrasonically treated to ensure thorough mixing and dissolution. It is then filtered with qualitative filter paper to obtain a clear solution. The solution is then sealed with a polyvinyl chloride film and placed in a static environment free from shaking, pollution, and air convection. Several small holes are punched in the seal to adjust the evaporation rate of the solvent in the solution. The solution is left to stand at room temperature. Subsequently, crystals precipitate out of the solution and gradually grow. Before the solvent has completely evaporated, the crystals are removed. The product in the polytetrafluoroethylene beaker is quickly washed with deionized water and placed on filter paper to dry. This yields a Cs2[C3H2O4]B(OH)3(H2O) nonlinear optical crystal with dimensions of 15mm×15mm×7mm.

[0139] Example 31

[0140] According to the reaction formula: C3H4O4 + H3BO3 + KBF4 + RbOH → KRb[C3H2O4]B(OH)3 + HBF4 + H2O↑, KRb[C3H2O4]B(OH)3 nonlinear optical crystal was prepared by room temperature solution method.

[0141] a. Mix C3H4O4, H3BO3, KBF4, and RbOH in a molar ratio of 1:1:1:1, add 50 mL of deionized water to fully mix and dissolve, and obtain a mixed solution;

[0142] b. The mixed solution from step a is ultrasonically treated to ensure thorough mixing and dissolution. It is then filtered with qualitative filter paper to obtain a clear solution. The solution is then sealed with a polyvinyl chloride film and placed in a static environment free from shaking, contamination, and air convection. Several small holes are punched in the seal to adjust the evaporation rate of the solvent in the solution. The solution is left to stand at room temperature. Subsequently, crystals precipitate out of the solution and gradually grow. Before the solvent has completely evaporated, the crystals are removed. The product in the polytetrafluoroethylene beaker is quickly washed with deionized water and placed on filter paper to dry. This yields a KRb[C3H2O4]B(OH)3 nonlinear optical crystal with dimensions of 20mm×15mm×8mm.

[0143] Example 32

[0144] According to the reaction formula: C3H4O4 + H3BO3 + KBF4 + CsOH → KCs[C3H2O4]B(OH)3 + HBF4 + H2O↑, KRb[C3H2O4]B(OH)3 nonlinear optical crystal was prepared by room temperature solution method.

[0145] a. Mix C3H4O4, H3BO3, KBF4, and CsOH in a molar ratio of 1:1:1:1, add 50 mL of deionized water to fully mix and dissolve, and obtain a mixed solution;

[0146] b. The mixed solution from step a is ultrasonically treated to ensure thorough mixing and dissolution. It is then filtered with qualitative filter paper to obtain a clear solution. The solution is then sealed with a polyvinyl chloride film and placed in a static environment free from shaking, pollution, and air convection. Several small holes are punched in the seal to adjust the evaporation rate of the solvent in the solution. The solution is left to stand at room temperature. Subsequently, crystals precipitate out of the solution and gradually grow. Before the solvent has completely evaporated, the crystals are removed. The product in the polytetrafluoroethylene beaker is quickly washed with deionized water and placed on filter paper to dry. This yields a KCs[C3H2O4]B(OH)3 nonlinear optical crystal with dimensions of 21mm×15mm×7mm.

[0147] Example 33

[0148] According to the reaction formula: C3H4O4+H3BO3+RbBF4+KOH→KRb[C3H2O4]B(OH)3+HBF4+H2O↑, KRb[C3H2O4]B(OH)3 nonlinear optical crystal was prepared by room temperature solution method.

[0149] a. Mix C3H4O4, H3BO3, RbBF4, and KOH evenly in a molar ratio of 1:1:1:1, add 50 mL of deionized water to fully mix and dissolve, and obtain a mixed solution;

[0150] b. The mixed solution from step a is ultrasonically treated to ensure thorough mixing and dissolution. It is then filtered with qualitative filter paper to obtain a clear solution. The solution is then sealed with a polyvinyl chloride film and placed in a static environment free from shaking, pollution, and air convection. Several small holes are punched in the seal to adjust the evaporation rate of the solvent in the solution. The solution is left to stand at room temperature. Subsequently, crystals precipitate out of the solution and gradually grow. Before the solvent has completely evaporated, the crystals are removed. The product in the polytetrafluoroethylene beaker is quickly washed with deionized water and placed on filter paper to dry. This yields a KRb[C3H2O4]B(OH)3 nonlinear optical crystal with dimensions of 16mm×14mm×10mm.

[0151] Example 34

[0152] According to the reaction formula: C3H4O4 + H3BO3 + CsBF4 + KOH → KCs[C3H2O4]B(OH)3 + HBF4 + H2O↑, KCs[C3H2O4]B(OH)3 nonlinear optical crystal was prepared by room temperature solution method.

[0153] a. Mix C3H4O4, H3BO3, CsBF4, and KOH evenly in a molar ratio of 1:1:1:1, add 50mL of deionized water to fully mix and dissolve, and obtain a mixed solution;

[0154] b. The mixed solution from step a is ultrasonically treated to ensure thorough mixing and dissolution. It is then filtered with qualitative filter paper to obtain a clear solution. The solution is then sealed with a polyvinyl chloride film and placed in a static environment free from shaking, pollution, and air convection. Several small holes are punched in the seal to adjust the evaporation rate of the solvent in the solution. The solution is left to stand at room temperature. Subsequently, crystals precipitate out of the solution and gradually grow. Before the solvent has completely evaporated, the crystals are removed. The product in the polytetrafluoroethylene beaker is quickly washed with deionized water and placed on filter paper to dry. This yields a KCs[C3H2O4]B(OH)3 nonlinear optical crystal with dimensions of 18mm×17mm×9mm.

[0155] Example 35

[0156] According to the reaction formula: C3H4O4+H3BO3+RbBF4+CsOH→RbCs[C3H2O4]B(OH)3+HBF4+H2O↑, RbCs[C3H2O4]B(OH)3 nonlinear optical crystal was prepared by room temperature solution method.

[0157] a. Mix C3H4O4, H3BO3, RbBF4, and CsOH in a molar ratio of 1:1:1:1, add 50 mL of deionized water to fully mix and dissolve, and obtain a mixed solution;

[0158] b. The mixed solution from step a is ultrasonically treated to ensure thorough mixing and dissolution. It is then filtered with qualitative filter paper to obtain a clear solution. The solution is then sealed with a polyvinyl chloride film and placed in a static environment free from shaking, pollution, and air convection. Several small holes are punched in the seal to adjust the evaporation rate of the solvent in the solution. The solution is left to stand at room temperature. Subsequently, crystals precipitate out of the solution and gradually grow. Before the solvent has completely evaporated, the crystals are removed. The product in the polytetrafluoroethylene beaker is quickly washed with deionized water and placed on filter paper to dry. This yields a RbCs[C3H2O4]B(OH)3 nonlinear optical crystal with dimensions of 19mm×16mm×8mm.

[0159] Example 36

[0160] According to the reaction formula: C3H4O4 + H3BO3 + CsBF4 + RbOH → RbCs[C3H2O4]B(OH)3 + HBF4 + H2O↑, RbCs[C3H2O4]B(OH)3 nonlinear optical crystal was prepared by room temperature solution method.

[0161] a. Mix C3H4O4, H3BO3, CsBF4, and RbOH in a molar ratio of 1:1:1:1, add 50 mL of deionized water to fully mix and dissolve, and obtain a mixed solution;

[0162] b. The mixed solution from step a is ultrasonically treated to ensure thorough mixing and dissolution. It is then filtered with qualitative filter paper to obtain a clear solution. The solution is then sealed with a polyvinyl chloride film and placed in a static environment free from shaking, pollution, and air convection. Several small holes are punched in the seal to adjust the evaporation rate of the solvent in the solution. The solution is left to stand at room temperature. Subsequently, crystals precipitate out of the solution and gradually grow. Before the solvent has completely evaporated, the crystals are removed. The product in the polytetrafluoroethylene beaker is quickly washed with deionized water and placed on filter paper to dry. This yields a RbCs[C3H2O4]B(OH)3 nonlinear optical crystal with dimensions of 22mm×17mm×10mm.

[0163] Example 37

[0164] Any AM[C3H2O4]B(OH)3(H2O) obtained in Examples 1-36 x Nonlinear optical crystals are processed according to matching directions, and according to the attached... Figure 3 As shown, the device is positioned at location 3. At room temperature, a Q-switched Nd:YAG laser is used as the light source, with an incident wavelength of 1064 nm. An infrared beam 2 with a wavelength of 1064 nm emitted from the Q-switched Nd:YAG laser 1 is incident on AM[C3H2O4]B(OH)3(H2O). xSingle crystal 3 produces green frequency-doubled light with a wavelength of 532nm, and the output intensity is about 0.5-1.2 times that of KDP under the same conditions; the emitted beam 4 contains infrared light with a wavelength of 1064nm and green light with a wavelength of 532nm, which are filtered out by filter 5 to obtain green laser with a wavelength of 532nm.

Claims

1. A series of malonate borate nonlinear optical crystals, characterized in that, The general molecular formula of this crystal is AM[C3H2O4]B(OH)3(H2O). x Where A = K, Rb, Cs, M = K, Rb, Cs, x = 0, 1, it has no center of symmetry, orthorhombic crystal system, space group P 212121, Cell parameters: 1) K2[C3H2O4]B(OH)3: a = 6.6168(11) Å, b = 9.574(5) Å, c = 13.0172(12) Å, α = 90, β = 90, γ = 90, Z = 4, V = 851.3(4) Å 3 ; 2) KRb[C3H2O4]B(OH)3: a = 6.6768(13) Å, b = 9.7841(2) Å, c = 13.2670(19) Å, α = 90, β = 90, γ =90, Z = 4, V = 866.7(3) Å 3 ; 3) KCs[C3H2O4]B(OH)3: a = 6.8643(7) Å, b = 9.7528(11) Å, c = 13.5427(16) Å, α = 90, β = 90, γ = 90, Z = 4, V = 906.63(17) Å 3 ; 4) Rb2[C3H2O4]B(OH)3: a = 6.7628(10) Å, b = 9.9512(14) Å, c = 13.5436(15) Å, α = 90, β = 90, γ =90, Z = 4, V = 911.5(2) Å 3 ; 5) RbCs[C3H2O4]B(OH)3: a = 6.9734(7) Å, b = 9.811(4) Å, c = 13.6132(12) Å, α = 90, β = 90, γ = 90, Z = 4, V = 923.4(3) Å 3 ; 6) Cs2[C3H2O4]B(OH)3(H2O): a = 7.256(3) Å, b = 10.271(3) Å, c = 13.984(5) Å, α = 90, β = 90, γ =90, Z = 4,V = 1042.2(7) Å 3 。 2. The method for preparing the series of malonate borate nonlinear optical crystals according to claim 1, characterized in that... Crystals are grown using the room temperature solution method, and the specific procedures are as follows: a. Mix the following compounds in a molar ratio of 1:1:0.5-2:0-1: C3H4O4 (containing malonic acid ester); H3BO3 (containing boron); K2CO3, Rb2CO3, Cs2CO3, KOH, RbOH, CsOH, KBF4, RbBF4 or CsBF4 (containing cation A); and K2CO3, Rb2CO3, Cs2CO3, KOH, RbOH, CsOH, KBF4, RbBF4 or CsBF4 (containing cation M) thoroughly. Add 30-50 mL of deionized water to fully mix and dissolve the mixture to obtain a solution. b. The mixed solution from step a is ultrasonically treated to ensure thorough mixing and dissolution. Filter the solution using qualitative filter paper to obtain a clear solution. Seal the solution with a polyvinyl chloride film and place it in a static environment free from shaking, pollution, and air convection. Make several small holes in the seal to adjust the evaporation rate of the solvent in the solution. Let it stand at room temperature. Subsequently, crystals precipitate and gradually grow in the solution. Before the solvent has completely evaporated, remove the crystals and place them on filter paper to dry. This yields a series of nonlinear optical crystals of malonate borate, rubidium malonate borate, cesium malonate borate, rubidium malonate borate, rubidium malonate borate, or cesium malonate borate, with centimeter-sized crystals.

3. The use of the series of malonate borate nonlinear optical crystals according to claim 1 in the fabrication of multi-band frequency doubling devices or optical elements.

4. The use of the series of malonate borate nonlinear optical crystals according to claim 1 in preparing harmonic light output of the 1064 nm fundamental frequency light output by Nd:YAG laser, wherein the output intensity is approximately 0.5-1.2 times that of KDP under the same conditions.

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