Series of malonate borate nonlinear optical crystals as well as preparation method and application thereof

Abstract

The invention relates to a series of malonate borate nonlinear optical crystals as well as a preparation method and application thereof, the molecular general formula of the series of compounds is AM [C3H2O4] B (OH) 3 (H2O) x, in which A is K, Rb or Cs; m is K, Rb or Cs, x is 0 or 1, the molecular weight is 242.08-436.72, a room temperature solution method is adopted for preparation, an orthorhombic crystal system is adopted, the space group is P212121 (No.19), and the cell parameters are as follows: a is 6.6168 (11)-7.256 (3), b is 9.574 (5)-10.271 (3), c is 130172 (12)-13.984 (5), alpha is 90, beta is 90, gamma is 90, Z is 4, and V is 851.3 (4)-1042.2 (7) 3. The series of compound malonate borate nonlinear optical crystals obtained through the method have the advantages of being wide in light-transmitting wave band, stable in physical and chemical performance, moderate in mechanical hardness, not prone to fragmentation, easy to cut, polish and store and the like, green frequency doubling light with the wavelength of 532 nm can be generated when an infrared light beam of 1064 nm enters the AM [C3H2O4] B (OH) 3 (H2O) x crystal, and the infrared light beam of 1064 nm enters the AM [C3H2O4] B (OH) 3 (H2O) x crystal. And the output intensity is about 0.5-1.2 times of that of KDP under the same condition.

Description

Technical Field

[0001] The invention relates to a series of malonate borate nonlinear optical crystals, a preparation method and an application thereof. Background Art

[0002] Ultraviolet nonlinear optical materials are key materials for solid-state lasers to generate ultraviolet coherent light. In order to obtain nonlinear optical materials with nonlinear optical properties, the commonly used method internationally is to introduce nonlinear optical functional elements that are prone to distortion into the structure. These elements mainly contain d 0 , d 10 The electronic structure of the transition metal cation polyhedron or the metal cation polyhedron containing lone electron pairs. However, these structural elements often cause the ultraviolet cutoff edge of the material to red-shift, making it unusable in the ultraviolet region. The characteristic of borates is that they are conducive to the transmission of ultraviolet radiation. Many excellent nonlinear optical crystals have been found in borates, such as BBO (β-BBO), LBO (LiB3O5) crystals, CBO (CsB3O5) crystals, CLBO (CsLiB6O 10 ) crystals and KBBF (KBe₂BO₃F₂) crystals. Although the crystal growth technology for these materials has become increasingly mature, they still have significant shortcomings: easy deliquesce, long growth cycles, severe layered growth habits, and high cost. Therefore, synthesizing new nonlinear optical crystal materials remains a very important and arduous task. Summary of the Invention

[0003] The present invention aims to provide a series of malonate ester borate AM[C3H2O4]B(OH)3(H2O) x A nonlinear optical crystal, wherein A=K, Rb, Cs, M=K, Rb, Cs, x=0, 1, having no center of symmetry, an orthorhombic crystal system, a space group P212121 (No. 19), and unit 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 object of the present invention is to provide a method for preparing a series of malonate borate nonlinear optical crystals, which is prepared by a room temperature solution method.

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

[0006] The present invention discloses a series of malonate borate nonlinear optical crystals, the 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 symmetry center, orthorhombic system, space group P212121, unit 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 series of malonate borate nonlinear optical crystals adopts a room temperature solution method to grow the crystals. The specific operation is carried out according to the following steps:

[0008] a. Mix the malonate-containing compound C3H4O4; the boron-containing compound H3BO3; the cation A-containing compound K2CO3, Rb2CO3, Cs2CO3, KOH, RbOH, CsOH, KBF4, RbBF4 or CsBF4; and the cation M-containing compound K2CO3, Rb2CO3, Cs2CO3, KOH, RbOH, CsOH, KBF4, RbBF4 or CsBF4 in a molar ratio of 1:1:0.5-2:0-1, and add 30-50 mL of deionized water to fully mix and dissolve them to obtain a mixed solution;

[0009] b. Ultrasonic treatment of the mixed solution in step a to fully mix and dissolve it, filtering it with qualitative filter paper to obtain a clear solution, and then sealing it with a polyvinyl chloride film. The solution is placed in a static environment without shaking, pollution, or air convection, and a plurality of small holes are punched in the seal to adjust the volatilization rate of the solvent in the solution. The solution is allowed to stand at room temperature, and crystals are subsequently precipitated and gradually grow in the solution. When the solvent has not completely evaporated, the crystals are taken out and placed on filter paper to dry, thereby obtaining a series of centimeter-sized malonate borate nonlinear optical crystals of potassium malonate borate, potassium rubidium malonate borate, potassium cesium malonate borate, rubidium malonate borate, rubidium malonate borate, or cesium malonate borate.

[0010] The series of malonate borate nonlinear optical crystals are used in preparing multi-band frequency doubling devices or optical elements.

[0011] The series of malonate borate nonlinear optical crystals are used in preparing harmonic light output of 1064nm fundamental frequency light output by Nd:YAG laser for frequency doubling or tripling, and the output intensity is about 0.5-1.2 times that of KDP under the same conditions.

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

[0013] The preparation method of the series malonate borate nonlinear optical crystals of the present invention is to obtain a series of AM[C3H2O4]B(OH)3(H2O) with a size of centimeters. x Nonlinear optical crystals have no obvious layered growth habits. By using large-sized containers and extending the crystal growth cycle, correspondingly large-sized nonlinear optical crystals AM[C3H2O4]B(OH)3(H2O) can be obtained. x , in the series AM[C3H2O4]B(OH)3(H2O) xDuring the growth of nonlinear optical crystals, the crystals tend to grow transparent and without wrapping, and have the advantages of fast growth rate, low cost, and easy acquisition of large-sized crystals.

[0014] The large-size series AM[C3H2O4]B(OH)3(H2O) obtained by the method of the present invention x Nonlinear optical crystals can be used as nonlinear optical devices by orienting the crystal blank according to the crystallographic data, cutting the crystal according to the required angle, thickness and cross-sectional size, and polishing the light-transmitting surface of the crystal. This series of AM[C3H2O4]B(OH)3(H2O) x Nonlinear optical crystals have the advantages of a wide light transmission band, stable physical and chemical properties, moderate mechanical hardness, not easy to break, easy to cut, polish and preserve. BRIEF DESCRIPTION OF THE DRAWINGS

[0015] Figure 1 The compound of the present invention 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 AM[C3H2O4]B(OH)3(H2O) of the present invention x (A=K, Rb, Cs, M=K, Rb, Cs, x=0, 1) crystal structure diagram.

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

[0018] The present invention is described in detail below 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↑, K2[C3H2O4]B(OH)3 nonlinear optical crystal was prepared by room temperature solution method:

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

[0022] b. Ultrasonic treatment is performed on the mixed solution in step a to fully mix and dissolve it, and the solution is 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 without shaking, pollution, or air convection. Several small holes are punched in the seal to adjust the volatilization rate of the solvent in the solution. The solution is allowed to stand at room temperature, and crystals are subsequently precipitated and gradually grow in the solution. The crystals are taken out when the solvent has not completely evaporated. The product in the polytetrafluoroethylene beaker is quickly rinsed with deionized water and placed on filter paper to dry, thereby obtaining a K2[C3H2O4]B(OH)3 nonlinear optical crystal with a size of 18 mm×18 mm×8 mm.

[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 crystal was prepared by room temperature solution method:

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

[0026] b. Ultrasonic treatment is performed on the mixed solution in step a to fully mix and dissolve it, and the solution is 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 without shaking, pollution, or air convection. Several small holes are punched in the seal to adjust the volatilization rate of the solvent in the solution. The solution is allowed to stand at room temperature, and crystals are subsequently precipitated and gradually grow in the solution. The crystals are taken out when the solvent has not completely evaporated, and the product in the polytetrafluoroethylene beaker is quickly rinsed with deionized water and placed on filter paper to dry, thereby obtaining a KRb[C3H2O4]B(OH)3 nonlinear optical crystal with a size of 18 mm×17 mm×10 mm.

[0027] Example 3

[0028] According to the reaction formula: C3H4O4+H3BO3+0.5K2CO3+0.5Cs2CO3→KCs[C3H2O4]B(OH)3+CO2↑+H2O↑, KCs[C3H2O4]B(OH)3 nonlinear optical crystal was prepared by room temperature solution method:

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

[0030] b. Ultrasonicate the mixed solution in step a to fully mix and dissolve it, filter it with qualitative filter paper to obtain a clear solution, seal it with a polyvinyl chloride film, place it in a static environment without shaking, pollution, or air convection, poke several small holes in the seal to adjust the volatilization rate of the solvent in the solution, let it stand at room temperature, and then crystals will precipitate and gradually grow in the solution. Take out the crystals when the solvent has not completely evaporated, quickly rinse the product in the polytetrafluoroethylene beaker with deionized water, and place it on filter paper to dry, thereby obtaining a KCs[C3H2O4]B(OH)3 nonlinear optical crystal with a size of 21 mm×16 mm×11 mm.

[0031] Example 4

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

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

[0034] b. Ultrasonicate the mixed solution in step a to fully mix and dissolve it, filter it with qualitative filter paper to obtain a clear solution, seal it with a polyvinyl chloride film, and place it in a static environment without shaking, pollution, or air convection. Punch a number of small holes in the seal to adjust the volatilization rate of the solvent in the solution. Let it stand at room temperature, and then crystals will precipitate from the solution and gradually grow. Take out the crystals when the solvent has not completely evaporated, quickly rinse the product in the polytetrafluoroethylene beaker with deionized water, and place it on filter paper to dry, thereby obtaining a Rb2[C3H2O4]B(OH)3 nonlinear optical crystal with a size of 19 mm×14 mm×7 mm.

[0035] Example 5

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

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

[0038] b. Ultrasonicate the mixed solution in step a to fully mix and dissolve it, filter it with qualitative filter paper to obtain a clear solution, seal it with a polyvinyl chloride film, place it in a static environment without shaking, pollution, or air convection, poke several small holes in the seal to adjust the volatilization rate of the solvent in the solution, and let it stand at room temperature. Subsequently, crystals in the solution precipitate and gradually grow. Remove the crystals before the solvent is completely evaporated, quickly rinse the product in the polytetrafluoroethylene beaker with deionized water, and place it on filter paper to dry, thereby obtaining a RbCs[C3H2O4]B(OH)3 nonlinear optical crystal with a size of 18 mm×11 mm×6 mm.

[0039] Example 6

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

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

[0042] b. Ultrasonicate the mixed solution in step a to fully mix and dissolve it, filter it with qualitative filter paper to obtain a clear solution, seal it with a polyvinyl chloride film, and place it in a static environment without shaking, pollution, or air convection. Punch a number of small holes in the seal to adjust the volatilization rate of the solvent in the solution. Let it stand at room temperature, and then crystals will precipitate and gradually grow in the solution. Take out the crystals when the solvent has not completely evaporated, quickly rinse the product in the polytetrafluoroethylene beaker with deionized water, and place it on filter paper to dry, thereby obtaining a Cs2[C3H2O4]B(OH)3(H2O) nonlinear optical crystal with a size of 16 mm×14 mm×7 mm.

[0043] Example 7

[0044] According to the reaction formula: C3H4O4+H3BO3+0.5K2CO3+KOH→K2[C3H2O4]B(OH)3+0.5CO2↑+1.5H2O↑, 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, add 40 mL of deionized water to mix and dissolve them thoroughly to obtain a mixed solution.

[0046] b. Ultrasonicate the mixed solution in step a to fully mix and dissolve it, filter it with qualitative filter paper to obtain a clear solution, seal it with a polyvinyl chloride film, and place it in a static environment without shaking, pollution, or air convection. Punch a number of small holes in the seal to adjust the volatilization rate of the solvent in the solution. Let it stand at room temperature, and then crystals will precipitate and gradually grow in the solution. Take out the crystals when the solvent has not completely evaporated, quickly rinse the product in the polytetrafluoroethylene beaker with deionized water, and place it on filter paper to dry, thereby obtaining a K2[C3H2O4]B(OH)3 nonlinear optical crystal with a size of 14 mm×13 mm×9 mm.

[0047] Example 8

[0048] According to the reaction formula: C3H4O4+H3BO3+0.5Rb2CO3+RbOH→Rb2[C3H2O4]B(OH)3+0.5CO2↑+1.5H2O↑, 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, add 40 mL of deionized water to mix and dissolve them thoroughly to obtain a mixed solution.

[0050] b. Ultrasonicate the mixed solution in step a to fully mix and dissolve it, filter it with qualitative filter paper to obtain a clear solution, seal it with a polyvinyl chloride film, and place it in a static environment without shaking, pollution, or air convection. Punch a number of small holes in the seal to adjust the volatilization rate of the solvent in the solution. Let it stand at room temperature, and then crystals will precipitate and gradually grow in the solution. Take out the crystals when the solvent has not completely evaporated, quickly rinse the product in the polytetrafluoroethylene beaker with deionized water, and place it on filter paper to dry, thereby obtaining a Rb2[C3H2O4]B(OH)3 nonlinear optical crystal with a size of 18 mm×16 mm×8 mm.

[0051] Example 9

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

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

[0054] b. Ultrasonicate the mixed solution in step a to fully mix and dissolve it, filter it with qualitative filter paper to obtain a clear solution, seal it with a polyvinyl chloride film, and place it in a static environment without shaking, pollution, or air convection. Punch a number of small holes in the seal to adjust the volatilization rate of the solvent in the solution. Let it stand at room temperature, and then crystals will precipitate and gradually grow in the solution. Take out the crystals when the solvent has not completely evaporated, quickly rinse the product in the polytetrafluoroethylene beaker with deionized water, and place it on filter paper to dry, thereby obtaining a Cs2[C3H2O4]B(OH)3(H2O) nonlinear optical crystal with a size of 18 mm×16 mm×9 mm.

[0055] Example 10

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

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

[0058] b. Ultrasonicate the mixed solution in step a to fully mix and dissolve it, filter it with qualitative filter paper to obtain a clear solution, seal it with a polyvinyl chloride film, and place it in a static environment without shaking, pollution, or air convection. Punch a number of small holes in the seal to adjust the volatilization rate of the solvent in the solution. Let it stand at room temperature, and then crystals will precipitate and gradually grow in the solution. Take out the crystals when the solvent has not completely evaporated, quickly rinse the product in the polytetrafluoroethylene beaker with deionized water, and place it on filter paper to dry, thereby obtaining a K2[C3H2O4]B(OH)3 nonlinear optical crystal with a size of 19 mm×17 mm×7 mm.

[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 crystal was prepared by room temperature solution method:

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

[0062] b. Ultrasonicate the mixed solution in step a to fully mix and dissolve it, filter it with qualitative filter paper to obtain a clear solution, seal it with a polyvinyl chloride film, place it in a static environment without shaking, pollution, or air convection, poke several small holes in the seal to adjust the volatilization rate of the solvent in the solution, let it stand at room temperature, and then crystals will precipitate and gradually grow in the solution. Take out the crystals when the solvent has not completely evaporated, quickly rinse the product in the polytetrafluoroethylene beaker with deionized water, and place it on filter paper to dry, thereby obtaining a KRb[C3H2O4]B(OH)3 nonlinear optical crystal with a size of 17 mm×14 mm×6 mm.

[0063] Example 12

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

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

[0066] b. Ultrasonicate the mixed solution in step a to fully mix and dissolve it, filter it with qualitative filter paper to obtain a clear solution, seal it with a polyvinyl chloride film, place it in a static environment without shaking, pollution, or air convection, poke several small holes in the seal to adjust the volatilization rate of the solvent in the solution, let it stand at room temperature, and then crystals will precipitate and gradually grow in the solution. Take out the crystals when the solvent has not completely evaporated, quickly rinse the product in the polytetrafluoroethylene beaker with deionized water, and place it on filter paper to dry, thereby obtaining a KCs[C3H2O4]B(OH)3 nonlinear optical crystal with a size of 20 mm×12 mm×6 mm.

[0067] Example 13

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

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

[0070] b. Ultrasonicate the mixed solution in step a to fully mix and dissolve it, filter it with qualitative filter paper to obtain a clear solution, seal it with a polyvinyl chloride film, and place it in a static environment without shaking, pollution, or air convection. Punch a number of small holes in the seal to adjust the volatilization rate of the solvent in the solution. Let it stand at room temperature, and then crystals will precipitate from the solution and gradually grow. Take out the crystals when the solvent has not completely evaporated, quickly rinse the product in the polytetrafluoroethylene beaker with deionized water, and place it on filter paper to dry, thereby obtaining a Rb2[C3H2O4]B(OH)3 nonlinear optical crystal with a size of 21 mm × 15 mm × 8 mm.

[0071] Example 14

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

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

[0074] b. Ultrasonicate the mixed solution in step a to fully mix and dissolve it, filter it with qualitative filter paper to obtain a clear solution, seal it with a polyvinyl chloride film, place it in a static environment without shaking, pollution, or air convection, poke several small holes in the seal to adjust the volatilization rate of the solvent in the solution, and let it stand at room temperature. Subsequently, crystals in the solution precipitate and gradually grow. Remove the crystals before the solvent is completely evaporated, quickly rinse the product in the polytetrafluoroethylene beaker with deionized water, and place it on filter paper to dry, thereby obtaining a RbCs[C3H2O4]B(OH)3 nonlinear optical crystal with a size of 17 mm×15 mm×6 mm.

[0075] Example 15

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

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

[0078] b. Ultrasonicate the mixed solution in step a to fully mix and dissolve it, filter it with qualitative filter paper to obtain a clear solution, seal it with a polyvinyl chloride film, and place it in a static environment without shaking, pollution, or air convection. Punch a number of small holes in the seal to adjust the volatilization rate of the solvent in the solution. Let it stand at room temperature, and then crystals will precipitate and gradually grow in the solution. Take out the crystals when the solvent has not completely evaporated, quickly rinse the product in the polytetrafluoroethylene beaker with deionized water, and place it on filter paper to dry, thereby obtaining a Cs2[C3H2O4]B(OH)3(H2O) nonlinear optical crystal with a size of 17 mm×12 mm×7 mm.

[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 in a molar ratio of 1:1:0.5:1, and add 40 mL of deionized water to mix and dissolve them thoroughly to obtain a mixed solution;

[0082] b. Ultrasonicate the mixed solution in step a to fully mix and dissolve it, filter it with qualitative filter paper to obtain a clear solution, seal it with a polyvinyl chloride film, and place it in a static environment without shaking, pollution, or air convection. Punch a number of small holes in the seal to adjust the volatilization rate of the solvent in the solution. Let it stand at room temperature, and then crystals will precipitate and gradually grow in the solution. Take out the crystals when the solvent has not completely evaporated, quickly rinse the product in the polytetrafluoroethylene beaker with deionized water, and place it on filter paper to dry, thereby obtaining a KRb[C3H2O4]B(OH)3 nonlinear optical crystal with a size of 22 mm×16 mm×10 mm.

[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 in a molar ratio of 1:1:0.5:1, and add 40 mL of deionized water to mix and dissolve them thoroughly to obtain a mixed solution;

[0086] b. Ultrasonicate the mixed solution in step a to fully mix and dissolve it, filter it with qualitative filter paper to obtain a clear solution, seal it with a polyvinyl chloride film, place it in a static environment without shaking, pollution, or air convection, poke several small holes in the seal to adjust the volatilization rate of the solvent in the solution, let it stand at room temperature, and then crystals will precipitate and gradually grow in the solution. Take out the crystals when the solvent has not completely evaporated, quickly rinse the product in the polytetrafluoroethylene beaker with deionized water, and place it on filter paper to dry, thereby obtaining a KRb[C3H2O4]B(OH)3 nonlinear optical crystal with a size of 20 mm×15 mm×10 mm.

[0087] Example 18

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

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

[0090] b. Ultrasonicate the mixed solution in step a to fully mix and dissolve it, filter it with qualitative filter paper to obtain a clear solution, seal it with a polyvinyl chloride film, place it in a static environment without shaking, pollution, or air convection, poke several small holes in the seal to adjust the volatilization rate of the solvent in the solution, let it stand at room temperature, and then crystals will precipitate and gradually grow in the solution. Take out the crystals when the solvent has not completely evaporated, quickly rinse the product in the polytetrafluoroethylene beaker with deionized water, and place it on filter paper to dry, thereby obtaining a KCs[C3H2O4]B(OH)3 nonlinear optical crystal with a size of 22 mm×16 mm×10 mm.

[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 in a molar ratio of 1:1:0.5:1, and add 40 mL of deionized water to mix and dissolve them thoroughly to obtain a mixed solution;

[0094] b. Ultrasonicate the mixed solution in step a to fully mix and dissolve it, filter it with qualitative filter paper to obtain a clear solution, seal it with a polyvinyl chloride film, and place it in a static environment without shaking, pollution, or air convection. Punch a number of small holes in the seal to adjust the volatilization rate of the solvent in the solution. Let it stand at room temperature, and then crystals will precipitate and gradually grow in the solution. Take out the crystals before the solvent is completely evaporated, quickly rinse the product in the polytetrafluoroethylene beaker with deionized water, and place it on filter paper to dry, thereby obtaining a KCs[C3H2O4]B(OH)3 nonlinear optical crystal with a size of 19 mm×17 mm×10 mm.

[0095] Example 20

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

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

[0098] b. Ultrasonicate the mixed solution in step a to fully mix and dissolve it, filter it with qualitative filter paper to obtain a clear solution, seal it with a polyvinyl chloride film, and place it in a static environment without shaking, pollution, or air convection. Punch a number of small holes in the seal to adjust the volatilization rate of the solvent in the solution. Let it stand at room temperature, and then crystals will precipitate and gradually grow in the solution. Remove the crystals before the solvent is completely evaporated, quickly rinse the product in the polytetrafluoroethylene beaker with deionized water, and place it on filter paper to dry, thereby obtaining a RbCs[C3H2O4]B(OH)3 nonlinear optical crystal with a size of 18 mm×17 mm×10 mm.

[0099] Example 21

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

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

[0102] b. Ultrasonicate the mixed solution in step a to fully mix and dissolve it, filter it with qualitative filter paper to obtain a clear solution, seal it with a polyvinyl chloride film, place it in a static environment without shaking, pollution, or air convection, poke several small holes in the seal to adjust the volatilization rate of the solvent in the solution, and let it stand at room temperature. Subsequently, crystals in the solution precipitate and gradually grow. Remove the crystals before the solvent is completely evaporated, quickly rinse the product in the polytetrafluoroethylene beaker with deionized water, and place it on filter paper to dry, thereby obtaining a RbCs[C3H2O4]B(OH)3 nonlinear optical crystal with a size of 19 mm×16 mm×9 mm.

[0103] Example 22

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

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

[0106] b. Ultrasonicate the mixed solution in step a to fully mix and dissolve it, filter it with qualitative filter paper to obtain a clear solution, seal it with a polyvinyl chloride film, place it in a static environment without shaking, pollution, or air convection, poke several small holes in the seal to adjust the volatilization rate of the solvent in the solution, let it stand at room temperature, and then crystals will precipitate and gradually grow in the solution. Take out the crystals when the solvent has not completely evaporated, quickly rinse the product in the polytetrafluoroethylene beaker with deionized water, and place it on filter paper to dry, thereby obtaining a K2[C3H2O4]B(OH)3 nonlinear optical crystal with a size of 22 mm×18 mm×10 mm.

[0107] Example 23

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

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

[0110] b. Ultrasonicate the mixed solution in step a to fully mix and dissolve it, filter it with qualitative filter paper to obtain a clear solution, seal it with a polyvinyl chloride film, and place it in a static environment without shaking, pollution, or air convection. Punch a number of small holes in the seal to adjust the volatilization rate of the solvent in the solution. Let it stand at room temperature, and then crystals will precipitate from the solution and gradually grow. Take out the crystals when the solvent has not completely evaporated, quickly rinse the product in the polytetrafluoroethylene beaker with deionized water, and place it on filter paper to dry, thereby obtaining a Rb2[C3H2O4]B(OH)3 nonlinear optical crystal with a size of 20 mm × 15 mm × 9 mm.

[0111] Example 24

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

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

[0114] b. Ultrasonicate the mixed solution in step a to fully mix and dissolve it, filter it with qualitative filter paper to obtain a clear solution, seal it with a polyvinyl chloride film, and place it in a static environment without shaking, pollution, or air convection. Punch a number of small holes in the seal to adjust the volatilization rate of the solvent in the solution. Let it stand at room temperature, and then crystals will precipitate and gradually grow in the solution. Take out the crystals when the solvent has not completely evaporated, quickly rinse the product in the polytetrafluoroethylene beaker with deionized water, and place it on filter paper to dry, thereby obtaining a Cs2[C3H2O4]B(OH)3(H2O) nonlinear optical crystal with a size of 16 mm×13 mm×8 mm.

[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 in a molar ratio of 1:1:1:1, and add 50 mL of deionized water to mix and dissolve them thoroughly to obtain a mixed solution;

[0118] b. Ultrasonicate the mixed solution in step a to fully mix and dissolve it, filter it with qualitative filter paper to obtain a clear solution, seal it with a polyvinyl chloride film, and place it in a static environment without shaking, pollution, or air convection. Punch a number of small holes in the seal to adjust the volatilization rate of the solvent in the solution. Let it stand at room temperature, and then crystals will precipitate and gradually grow in the solution. Take out the crystals when the solvent has not completely evaporated, quickly rinse the product in the polytetrafluoroethylene beaker with deionized water, and place it on filter paper to dry, thereby obtaining a KRb[C3H2O4]B(OH)3 nonlinear optical crystal with a size of 19 mm×18 mm×10 mm.

[0119] Example 26

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

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

[0122] b. Ultrasonicate the mixed solution in step a to fully mix and dissolve it, filter it with qualitative filter paper to obtain a clear solution, seal it with a polyvinyl chloride film, and place it in a static environment without shaking, pollution, or air convection. Punch a number of small holes in the seal to adjust the volatilization rate of the solvent in the solution. Let it stand at room temperature, and then crystals will precipitate and gradually grow in the solution. Take out the crystals before the solvent is completely evaporated, quickly rinse the product in the polytetrafluoroethylene beaker with deionized water, and place it on filter paper to dry, thereby obtaining a KCs[C3H2O4]B(OH)3 nonlinear optical crystal with a size of 21 mm×19 mm×10 mm.

[0123] Example 27

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

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

[0126] b. Ultrasonicate the mixed solution in step a to fully mix and dissolve it, filter it with qualitative filter paper to obtain a clear solution, seal it with a polyvinyl chloride film, place it in a static environment without shaking, pollution, or air convection, poke several small holes in the seal to adjust the volatilization rate of the solvent in the solution, and let it stand at room temperature. Subsequently, crystals in the solution precipitate and gradually grow. Remove the crystals before the solvent is completely evaporated, quickly rinse the product in the polytetrafluoroethylene beaker with deionized water, and place it on filter paper to dry, thereby obtaining a RbCs[C3H2O4]B(OH)3 nonlinear optical crystal with a size of 20 mm×16 mm×8 mm.

[0127] Example 28

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

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

[0130] b. Ultrasonicate the mixed solution in step a to fully mix and dissolve it, filter it with qualitative filter paper to obtain a clear solution, seal it with a polyvinyl chloride film, and place it in a static environment without shaking, pollution, or air convection. Punch a number of small holes in the seal to adjust the volatilization rate of the solvent in the solution. Let it stand at room temperature, and then crystals will precipitate and gradually grow in the solution. Take out the crystals when the solvent has not completely evaporated, quickly rinse the product in the polytetrafluoroethylene beaker with deionized water, and place it on filter paper to dry, thereby obtaining a K2[C3H2O4]B(OH)3 nonlinear optical crystal with a size of 19 mm×15 mm×7 mm.

[0131] Example 29

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

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

[0134] b. Ultrasonicate the mixed solution in step a to fully mix and dissolve it, filter it with qualitative filter paper to obtain a clear solution, seal it with a polyvinyl chloride film, and place it in a static environment without shaking, pollution, or air convection. Punch a number of small holes in the seal to adjust the volatilization rate of the solvent in the solution. Let it stand at room temperature, and then crystals will precipitate from the solution and gradually grow. Take out the crystals when the solvent has not completely evaporated, quickly rinse the product in the polytetrafluoroethylene beaker with deionized water, and place it on filter paper to dry, thereby obtaining a Rb2[C3H2O4]B(OH)3 nonlinear optical crystal with a size of 20 mm×16 mm×8 mm.

[0135] Example 30

[0136] According to the reaction formula: C3H4O4+H3BO3+CsBF4+CsOH→Cs2[C3H2O4]B(OH)3(H2O)+HBF4, 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, and add 50 mL of deionized water to mix and dissolve them thoroughly to obtain a mixed solution;

[0138] b. Ultrasonicate the mixed solution in step a to fully mix and dissolve it, filter it with qualitative filter paper to obtain a clear solution, seal it with a polyvinyl chloride film, and place it in a static environment without shaking, pollution, or air convection. Punch a number of small holes in the seal to adjust the volatilization rate of the solvent in the solution. Let it stand at room temperature, and then crystals will precipitate and gradually grow in the solution. Take out the crystals when the solvent has not completely evaporated, quickly rinse the product in the polytetrafluoroethylene beaker with deionized water, and place it on filter paper to dry, thereby obtaining a Cs2[C3H2O4]B(OH)3(H2O) nonlinear optical crystal with a size of 15 mm×15 mm×7 mm.

[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, and add 50 mL of deionized water to mix and dissolve them thoroughly to obtain a mixed solution;

[0142] b. Ultrasonicate the mixed solution in step a to fully mix and dissolve it, filter it with qualitative filter paper to obtain a clear solution, seal it with a polyvinyl chloride film, place it in a static environment without shaking, pollution, or air convection, poke several small holes in the seal to adjust the volatilization rate of the solvent in the solution, let it stand at room temperature, and then crystals will precipitate and gradually grow in the solution. Take out the crystals when the solvent has not completely evaporated, quickly rinse the product in the polytetrafluoroethylene beaker with deionized water, and place it on filter paper to dry, thereby obtaining a KRb[C3H2O4]B(OH)3 nonlinear optical crystal with a size of 20 mm×15 mm×8 mm.

[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, and add 50 mL of deionized water to mix and dissolve them thoroughly to obtain a mixed solution;

[0146] b. Ultrasonicate the mixed solution in step a to fully mix and dissolve it, filter it with qualitative filter paper to obtain a clear solution, seal it with a polyvinyl chloride film, and place it in a static environment without shaking, pollution, or air convection. Punch a number of small holes in the seal to adjust the volatilization rate of the solvent in the solution. Let it stand at room temperature, and then crystals will precipitate and gradually grow in the solution. Take out the crystals before the solvent is completely evaporated, quickly rinse the product in the polytetrafluoroethylene beaker with deionized water, and place it on filter paper to dry, thereby obtaining a KCs[C3H2O4]B(OH)3 nonlinear optical crystal with a size of 21 mm×15 mm×7 mm.

[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 in a molar ratio of 1:1:1:1, and add 50 mL of deionized water to mix and dissolve them thoroughly to obtain a mixed solution;

[0150] b. Ultrasonicate the mixed solution in step a to fully mix and dissolve it, filter it with qualitative filter paper to obtain a clear solution, seal it with a polyvinyl chloride film, and place it in a static environment without shaking, pollution, or air convection. Punch a number of small holes in the seal to adjust the volatilization rate of the solvent in the solution. Let it stand at room temperature, and then crystals will precipitate and gradually grow in the solution. Take out the crystals when the solvent has not completely evaporated, quickly rinse the product in the polytetrafluoroethylene beaker with deionized water, and place it on filter paper to dry, thereby obtaining a KRb[C3H2O4]B(OH)3 nonlinear optical crystal with a size of 16 mm×14 mm×10 mm.

[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 in a molar ratio of 1:1:1:1, and add 50 mL of deionized water to mix and dissolve them thoroughly to obtain a mixed solution;

[0154] b. Ultrasonicate the mixed solution in step a to fully mix and dissolve it, filter it with qualitative filter paper to obtain a clear solution, seal it with a polyvinyl chloride film, and place it in a static environment without shaking, pollution, or air convection. Punch a number of small holes in the seal to adjust the volatilization rate of the solvent in the solution. Let it stand at room temperature, and then crystals will precipitate and gradually grow in the solution. Take out the crystals before the solvent is completely evaporated, quickly rinse the product in the polytetrafluoroethylene beaker with deionized water, and place it on filter paper to dry, thereby obtaining a KCs[C3H2O4]B(OH)3 nonlinear optical crystal with a size of 18 mm×17 mm×9 mm.

[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, and add 50 mL of deionized water to mix and dissolve them thoroughly to obtain a mixed solution;

[0158] b. Ultrasonicate the mixed solution in step a to fully mix and dissolve it, filter it with qualitative filter paper to obtain a clear solution, seal it with a polyvinyl chloride film, place it in a static environment without shaking, pollution, or air convection, poke several small holes in the seal to adjust the volatilization rate of the solvent in the solution, and let it stand at room temperature. Subsequently, crystals in the solution precipitate and gradually grow. Remove the crystals before the solvent is completely evaporated, quickly rinse the product in the polytetrafluoroethylene beaker with deionized water, and place it on filter paper to dry, thereby obtaining a RbCs[C3H2O4]B(OH)3 nonlinear optical crystal with a size of 19 mm×16 mm×8 mm.

[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, and add 50 mL of deionized water to mix and dissolve them thoroughly to obtain a mixed solution;

[0162] b. Ultrasonicate the mixed solution in step a to fully mix and dissolve it, filter it with qualitative filter paper to obtain a clear solution, seal it with a polyvinyl chloride film, place it in a static environment without shaking, pollution, or air convection, poke several small holes in the seal to adjust the volatilization rate of the solvent in the solution, and let it stand at room temperature. Subsequently, crystals in the solution precipitate and gradually grow. Remove the crystals before the solvent is completely evaporated, quickly rinse the product in the polytetrafluoroethylene beaker with deionized water, and place it on filter paper to dry, thereby obtaining a RbCs[C3H2O4]B(OH)3 nonlinear optical crystal with a size of 22 mm×17 mm×10 mm.

[0163] Example 37

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

Claims

1. A series of malonate borate nonlinear optical crystals, characterized in that: The molecular formula of the crystal 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 system, space group P 212121, unit 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 a series of malonate borate nonlinear optical crystals according to claim 1, characterized in that The room temperature solution method was used to grow crystals. The specific operation was carried out according to the following steps: a. Mix the malonate-containing compound C3H4O4; the boron-containing compound H3BO3; the cation A-containing compound K2CO3, Rb2CO3, Cs2CO3, KOH, RbOH, CsOH, KBF4, RbBF4 or CsBF4; and the cation M-containing compound K2CO3, Rb2CO3, Cs2CO3, KOH, RbOH, CsOH, KBF4, RbBF4 or CsBF4 in a molar ratio of 1:1:0.5-2:0-1, and add 30-50 mL of deionized water to fully mix and dissolve them to obtain a mixed solution; b. Ultrasonic treatment of the mixed solution in step a to fully mix and dissolve it, filtering it with qualitative filter paper to obtain a clear solution, and then sealing it with a polyvinyl chloride film. The solution is placed in a static environment without shaking, pollution, or air convection, and a plurality of small holes are punched in the seal to adjust the volatilization rate of the solvent in the solution. The solution is allowed to stand at room temperature, and crystals are subsequently precipitated and gradually grow in the solution. When the solvent has not completely evaporated, the crystals are taken out and placed on filter paper to dry, thereby obtaining a series of centimeter-sized malonate borate nonlinear optical crystals of potassium malonate borate, potassium rubidium malonate borate, potassium cesium malonate borate, rubidium malonate borate, rubidium malonate borate, or cesium malonate borate.

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

4. Use of the series of malonate borate nonlinear optical crystals according to claim 1 in preparing harmonic light output by frequency doubling or tripling the fundamental frequency light of 1064 nm output by an 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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