Series of compounds methane sulfonate and methane sulfonate nonlinear optical crystal and preparation method and use

Abstract

The present application relates to a series of compounds methane sulfonate and methane sulfonate nonlinear optical crystal and preparation method and use, the molecular general formula of the series of compounds is A3[CH3SO3]X2, wherein A=NH4, K, Rb, Cs, X=[NO3], Cl, Br, the molecular weight is 220.12-617.82, top seed method is prepared, orthorhombic system, space group Cmc 21 (No.36), the cell parameter is a=12.0014 (6) -12.5667 (2) Å, b=8.0324 (11) -8.4995 (1) Å, c=10.8823 (4) -11.3622 (15) Å, α =90, β =90, γ =90, Z =4, V=1048.4 (3) -1212.8 (2) Å 3 The series of compounds methane sulfonate nonlinear optical crystal obtained by the method has the advantages of wide light transmission waveband, stable physical and chemical properties, moderate mechanical hardness, not easy to break, easy to cut, polish processing and preservation and the like.

Description

TECHNICAL FIELD

[0001] The present application relates to a series of compounds methane sulfonate and methane sulfonate nonlinear optical crystal and preparation method and use. BACKGROUND

[0002] The ultraviolet nonlinear optical material is the key material for the ultraviolet coherent light generated by solid-state laser. In order to obtain the nonlinear optical material with nonlinear optical property, the commonly used method in the world at present is to introduce the nonlinear optical functional group which is easy to cause distortion in the structure. These groups mainly include the transition metal cation polyhedron with d 0 , d 10 electron structure or the metal cation polyhedron containing lone pair. However, these structure groups often cause the red shift of the ultraviolet cut-off edge of the material, so that it cannot be used in the ultraviolet region. The organic nonlinear optical crystal has high nonlinear optical coefficient, but its birefringence is too large, the acceptance angle is small, the nonlinear optical coefficient and the light transmission band are contradictory, and the low melting point and easy deliquescence limit its application. However, with the research on organic matters, many excellent nonlinear optical crystals have been found in organic matters at present, such as lithium monocarbonate (HCOOLi·H2O), urea (CO(NH2)2) crystal, dichlorodithiohydroxy cadmium crystal and phenylurea crystal. Although the crystal growth technology of these materials has become mature, there are still obvious deficiencies: such as easy deliquescence, long growth period, serious layered growth habit and high price. Therefore, it is still a very important and arduous work to synthesize new nonlinear optical crystal materials. SUMMARY

[0003] The present application aims at providing a series of compounds methane sulfonate, the molecular general formula of the compound is A3[CH3SO3]X2, wherein A = NH4, K, Rb, Cs, the molecular weight is 220.12-617.82, and top seed crystal method is adopted for preparation.

[0004] Another object of the present application is to provide a series of compounds methane sulfonate A3[CH3SO3]X2 nonlinear optical crystal, wherein A = NH4, K, Rb, Cs, X = [NO3], Cl, Br, without symmetry center, orthorhombic system, space group Cmc21 (No. 36), unit cell parameters: 1) (NH4)3[CH3SO3][NO3]2: α = 90, β = 90, γ = 90, Z = 4, 2) K3[CH3SO3][NO3]2: α = 90, β = 90, γ = 90, Z = 4, 3) Rb3[CH3SO3][NO3]2: α = 90, β = 90, γ = 90, Z = 4, 4) Cs3[CH3SO3][NO3]2: α = 90, β = 90, γ = 90, Z = 4, 5) (NH4)3[CH3SO3]Cl2: α = 90, β = 90, γ = 90, Z = 4, 6) K3[CH3SO3]Cl2: α = 90, β = 90, γ = 90, Z = 4, 7) Rb3[CH3SO3]Cl2: α = 90, β = 90, γ = 90, Z = 4, 8) Cs3[CH3SO3]Cl2: α = 90, β = 90, γ = 90, Z = 4, 9) (NH4)3[CH3SO3]Br2: α = 90, β = 90, γ = 90, Z = 4, 10) K3[CH3SO3]Br2: α = 90, β = 90, γ = 90, Z = 4, 11) Rb3[CH3SO3]Br2: α = 90, β = 90, γ = 90, Z = 4, 11) Cs3[CH3SO3]Br2: α = 90, β = 90, γ = 90, Z = 4,

[0005] Another objective of this invention is to provide a method for preparing a series of nonlinear optical crystals of methane sulfonate compounds, using a top seed crystal method to grow the crystals.

[0006] Another object of the present invention is to provide the use of a series of compounds, methane sulfonate A3[CH3SO3]X2, in nonlinear optical crystals.

[0007] The present invention discloses a series of methane sulfonates, which have the general molecular formula A3[CH3SO3]X2, wherein A = NH4, K, Rb, Cs, X = [NO3], Cl, Br, and have a molecular weight of 207.86-641.37, and are prepared by the top seed crystal method.

[0008] A series of nonlinear optical crystals containing methane sulfonates, the general molecular formula of which is A3[CH3SO3]X2, where A = NH4, K, Rb, Cs, X = [NO3], Cl, Br, lacks a center of symmetry, belongs to an orthorhombic crystal system, space group Cmc21 (No. 36), and has the following cell parameters: 1)(NH4)3[CH3SO3][NO3]2. α=90, β=90, γ=90, Z=4, 2) K3[CH3SO3][NO3]2: α=90, β=90, γ=90, Z=4, 3)

[0009] Rb3[CH3SO3][NO3]2: α=90, β=90, γ=90, Z=4, 4) Cs3[CH3SO3][NO3]2: α=90, β=90, γ=90, Z=4, 5)(NH4)3[CH3SO3]Cl2: α=90, β=90, γ=90, Z=4, 6) K3[CH3SO3]Cl2: α=90, β=90, γ=90, Z=4, 7) Rb3[CH3SO3]Cl2: α = 90, β = 90, γ = 90, Z = 4, 8) Cs3[CH3SO3]Cl2: α = 90, β = 90, γ = 90, Z = 4, 9) (NH4)3[CH3SO3]Br2: α = 90, β = 90, γ = 90, Z = 4, 10) K3[CH3SO3]Br2: α = 90, β = 90, γ = 90, Z = 4, 11) Rb3[CH3SO3]Br2: α = 90, β = 90, γ = 90, Z = 4, 12) Cs3[CH3SO3]Br2: α = 90, β = 90, γ = 90, Z = 4,

[0010] The preparation method of the series of methane sulfonate nonlinear optical crystals, top seed crystal method is adopted, and the specific operation is performed according to the following steps:

[0011] a. The ammonium, potassium, rubidium or cesium containing compound and methane sulfonic acid are mixed uniformly according to a molar ratio of 1:1-2, 0-50 mL of deionized water is added to fully mix and dissolve, to obtain a mixed solution, and the ammonium, potassium, rubidium or cesium containing compound is ammonium carbonate, potassium carbonate, rubidium carbonate, cesium carbonate, ammonium bicarbonate, potassium bicarbonate, rubidium bicarbonate, cesium bicarbonate, ammonia, potassium hydroxide, rubidium hydroxide or cesium hydroxide;

[0012] b. The mixed solution in step a is placed at constant temperature for 2-5 days, and the crystal is taken out when the solvent volatilizes to supersaturation and starts to precipitate, and is placed on filter paper to dry, to obtain a series of ammonium methane sulfonate, potassium methane sulfonate, rubidium methane sulfonate or cesium methane sulfonate containing methane sulfonic acid compounds;

[0013] c. mixing the methane sulfonic acid compound in step b with a nitric acid or halogen compound in a molar ratio of 1:2 and grinding uniformly, adding 50-150 mL of deionized water to make it fully mixed and dissolved to obtain a mixed solution, and the nitric acid or halogen compound is ammonium nitrate, potassium nitrate, rubidium nitrate, cesium nitrate, ammonium chloride, potassium chloride, rubidium chloride, cesium chloride, ammonium bromide, potassium bromide, rubidium bromide or cesium bromide;

[0014] or directly mixing the ammonium, potassium, rubidium or cesium containing compound, methane sulfonic acid and nitric acid or halogen containing compound in a molar ratio of 0.7-1.2:0.9-2.2:2-4 uniformly to obtain a mixture, adding 30-90 mL of deionized water to make it fully dissolved to obtain a mixed solution;

[0015] d. preparing the seed crystal of the series A3[CH3SO3]X2: placing the mixed solution in step c in a polytetrafluoroethylene beaker at a constant temperature for 2-5 days, then sealing with a polyvinyl chloride film, and placing in a static environment without shaking, pollution and air convection, and making a few small holes on the seal to adjust the evaporation rate of the solvent in the solution, and when the solution is saturated, the crystal begins to precipitate, and the crystal with good quality is taken out, which is the seed crystal of the compound A3[CH3SO3]X2;

[0016] e. fixing the seed crystal obtained in step d on the seed crystal rod, and lowering the seed crystal from the top of the aqueous solution crystal growth furnace to contact the surface of the saturated mixed solution in step d, heating the temperature of the mixed solution to 40-60℃, and rotating the seed crystal rod at a speed of 5-60 rpm to grow the crystal, and then lowering the temperature to room temperature at a rate of 0.5℃ / h, and then taking the crystal out of the solution, which is the nonlinear optical crystal of the series compound A3[CH3SO3]X2.

[0017] The series of compound methane sulfonic acid salt nonlinear optical crystal is used for preparing the 1064 nm fundamental frequency light output by the Nd:YAG laser to generate 2 times frequency or 3 times frequency or 4 times frequency harmonic light output.

[0018] The series of compound methane sulfonic acid salt nonlinear optical crystal is used for preparing a frequency doubling generator, an up or down frequency converter or an optical parametric oscillator.

[0019] The preparation method of the series of compound methane sulfonic acid salt nonlinear optical crystal, by which the centimeter level series of compound A3[CH3SO3]X2 nonlinear optical crystal is obtained, has no obvious layered growth habit, uses a large size container, and prolongs the growth period of the crystal, so that the corresponding large size nonlinear optical crystal A3[CH3SO3]X2 can be obtained, and the series of compound A3[CH3SO3]X2 nonlinear optical crystal is easy to grow large and transparent without wrapping, has the advantages of fast growth speed, low cost and easy to obtain large size crystal.

[0020] By using the method, the large-size series compound A3[CH3SO3]X2 nonlinear optical crystal obtained can be used as a nonlinear optical device after the crystal embryo is oriented according to crystallographic data of the crystal, the crystal is cut at a required angle, thickness and cross-sectional size, and the light transmission surface of the crystal is polished. BRIEF DESCRIPTION OF DRAWINGS

[0021] Figure 1 A powder XRD spectrum of the compound A3[CH3SO3]X2 (A = NH4, K, Rb, Cs, X = [NO3], Cl, Br) of the application;

[0022] Figure 2 A structure diagram of the A3[CH3SO3]X2 (A = NH4, K, Rb, Cs, X = [NO3], Cl, Br) crystal of the application;

[0023] Figure 3 A working principle diagram of a nonlinear optical device made of the A3[CH3SO3]X2 (A = NH4, K, Rb, Cs, X = [NO3], Cl, Br) crystal of the application, wherein 1 is a laser, 2 is a light beam, 3 is the A3[CH3SO3]X2 (A = NH4, K, Rb, Cs, X = [NO3], Cl, Br) crystal, 4 is an outgoing light beam, and 5 is a filter. DETAILED DESCRIPTION

[0024] Example 1

[0025] According to the reaction formula: 2NH4NO3+ NH4CH3SO3→ (NH4)3[CH3SO3][NO3]2, (NH4)3[CH3SO3][NO3]2 nonlinear optical crystal is synthesized by using a top seed method:

[0026] a. Ammonium carbonate (NH4)2CO3 and methane sulfonic acid are uniformly mixed in a molar ratio of 1:2 to obtain a mixture, and 50 ml of deionized water is added to fully dissolve the mixture to obtain a mixed solution; wherein the ammonium carbonate can be replaced by ammonium bicarbonate or ammonia water;

[0027] b. The mixed solution in step a is placed at a constant temperature for 4 days, and the crystal is taken out when the solvent volatilizes to supersaturation and starts to precipitate, and is placed on filter paper to dry, to obtain a methane sulfonic acid compound NH4CH3SO3;

[0028] c. Mixing NH4CH3SO3 obtained in step b with NH4NO3 in a molar ratio of 1:2 and grinding uniformly, adding 50 mL of deionized water to make it fully mixed and dissolved to obtain a mixed solution;

[0029] d. Preparing (NH4)3[CH3SO3][NO3]2 seed crystal: placing the mixed solution in step c in a constant temperature for 2 days, standing in a polytetrafluoroethylene beaker, sealing with a polyvinyl chloride film, and placing in a static environment without shaking, pollution, and air convection. A few small holes are made on the seal to adjust the evaporation rate of the solvent in the solution. When the solution is saturated, crystals begin to precipitate. The better quality crystals are taken out as (NH4)3[CH3SO3][NO3]2 seed crystal;

[0030] e. Fixing the seed crystal obtained in step d on the seed crystal rod, and lowering the seed crystal from the top of the aqueous solution crystal growth furnace to contact the surface of the saturated mixed solution prepared in step d. The temperature of the mixed solution is heated to 47°C, and the seed crystal rod is rotated at a speed of 10 rpm for crystal growth. After constant temperature for 3 days, the temperature is lowered to room temperature at a rate of 1.0°C / h. The crystals are taken out of the solution to obtain a 30 mm x 25 mm x 16 mm (NH4)3[CH3SO3][NO3]2 nonlinear optical crystal.

[0031] Example 2

[0032] According to the reaction formula: 2KNO3+KCH3SO3→K3[CH3SO3][NO3]2, K3[CH3SO3][NO3]2 nonlinear optical crystal is synthesized by top seed crystal method:

[0033] a. Mixing K2CO3 and methane sulfonic acid uniformly in a molar ratio of 1:2 to obtain a mixture, and adding 50 mL of deionized water to make it fully dissolved to obtain a mixed solution. The potassium carbonate can be replaced by potassium bicarbonate or potassium hydroxide;

[0034] b. Standing the mixed solution in step a in a constant temperature for 2 days. When the solvent is over-saturated and begins to precipitate crystals, the crystals are taken out before the solvent is completely evaporated and placed on filter paper to dry, obtaining methane sulfonic acid compound KCH3SO3;

[0035] c. Mixing KCH3SO3 obtained in step b with KNO3 in a molar ratio of 1:2 and grinding uniformly, adding 50 mL of deionized water to make it fully mixed and dissolved to obtain a mixed solution;

[0036] d. Preparation of compound K3[CH3SO3][NO3]2 seed crystal: the mixed solution in step c is kept constant for 3 days, and is placed in a polytetrafluoroethylene beaker, and is sealed with a polyvinyl chloride film, and is placed in a static environment without shaking, pollution, and air convection, a plurality of small holes are punched on the seal to adjust the evaporation rate of the solvent in the solution, and when the solution is saturated, crystals begin to precipitate, and the better quality crystals are taken out to obtain the compound K3[CH3SO3][NO3]2 seed crystal;

[0037] e. The seed crystal obtained in step d is fixed on a seed crystal rod, and the seed crystal is lowered from the top of the aqueous solution crystal growth furnace to contact the surface of the saturated mixed solution prepared in step d, the temperature of the mixed solution is heated to 47°C, the seed crystal rod is rotated at a speed of 12 rpm to grow crystals, and the temperature is kept constant for 3 days, and then the temperature is lowered to room temperature at a rate of 0.7°C / h, and then the crystals are taken out from the solution to obtain a K3[CH3SO3][NO3]2 nonlinear optical crystal with a size of 22mm x 21mm x 10mm.

[0038] Example 3

[0039] According to the reaction formula: 2RbNO3+RbCH3SO3→Rb3[CH3SO3][NO3]2, Rb3[CH3SO3][NO3]2 nonlinear optical crystal is synthesized by top seed method:

[0040] a. Rb2CO3 and methane sulfonic acid are uniformly mixed in a molar ratio of 1:2 to obtain a mixture, and 40 ml of deionized water is added to fully dissolve the mixture to obtain a mixed solution; wherein the rubidium carbonate can be replaced by rubidium bicarbonate or rubidium hydroxide;

[0041] b. The mixed solution in step a is kept constant for 2 days, and is placed in a polytetrafluoroethylene beaker, and is sealed with a polyvinyl chloride film, and is placed in a static environment without shaking, pollution, and air convection, a plurality of small holes are punched on the seal to adjust the evaporation rate of the solvent in the solution, and when the solution is saturated, crystals begin to precipitate, and the better quality crystals are taken out to obtain the compound K3[CH3SO3][NO3]2 seed crystal;

[0042] c. RbCH3SO3 obtained in step b is mixed with RbNO3 in a molar ratio of 1:2 and is ground uniformly, and 50 mL of deionized water is added to fully mix and dissolve the mixture to obtain a mixed solution;

[0043] d. Preparation of compound Rb3[CH3SO3][NO3]2 seed crystal: the mixed solution in step c is kept constant for 2 days, and is placed in a polytetrafluoroethylene beaker, and is sealed with a polyvinyl chloride film, and is placed in a static environment without shaking, pollution, and air convection, a plurality of small holes are punched on the seal to adjust the evaporation rate of the solvent in the solution, and when the solution is saturated, crystals begin to precipitate, and the better quality crystals are taken out to obtain the compound K3[CH3SO3][NO3]2 seed crystal;

[0044] e. Fixing the seed crystal obtained in step d on a seed crystal rod, lowering the seed crystal from the top of the aqueous solution crystal growth furnace to contact the surface of the saturated mixed solution prepared in step d, heating the mixed solution to a temperature of 45°C, rotating the seed crystal rod at a speed of 14 rpm to grow the crystal, maintaining the temperature for 3 days, then lowering the temperature to room temperature at a rate of 0.6°C / h, and then taking the crystal out of the solution to obtain a Rb3[CH3SO3][NO3]2 nonlinear optical crystal with a size of 14 mm x 13 mm x 10 mm.

[0045] Example 4

[0046] According to the reaction formula: 2CsNO3+ CsCH3SO3→ Cs3[CH3SO3][NO3]2, a Cs3[CH3SO3][NO3]2 nonlinear optical crystal is synthesized by a top-seeding method.

[0047] a. Mixing Cs2CO3 and methane sulfonic acid uniformly at a molar ratio of 1:2 to obtain a mixture, and adding 50 ml of deionized water to fully dissolve the mixture to obtain a mixed solution; wherein the cesium carbonate can be replaced by cesium bicarbonate or cesium hydroxide;

[0048] b. Placing the mixed solution in step a in a thermostat for 3 days, allowing the solvent to evaporate to supersaturation to start the crystal precipitation, taking the crystal out when the solvent has not completely evaporated, and placing the crystal on filter paper to dry, to obtain a methane sulfonic acid compound CsCH3SO3;

[0049] c. Mixing and grinding the CsCH3SO3 obtained in step b and CsNO3 uniformly at a molar ratio of 1:2, and adding 40 ml of deionized water to fully mix and dissolve the mixture to obtain a mixed solution;

[0050] d. Preparing a compound Cs3[CH3SO3][NO3]2 seed crystal: placing the mixed solution in step c in a polytetrafluoroethylene beaker in a thermostat for 3 days, sealing the beaker with a polyvinyl chloride film, placing the sealed beaker in a static environment without shaking, without pollution, and without air convection, making a few small holes on the seal to adjust the evaporation rate of the solvent in the solution, and taking out the crystal with good quality when the solution is saturated to obtain a compound Cs3[CH3SO3][NO3]2 seed crystal;

[0051] e. Fixing the seed crystal obtained in step d on a seed crystal rod, lowering the seed crystal from the top of the aqueous solution crystal growth furnace to contact the surface of the saturated mixed solution prepared in step d, heating the mixed solution to a temperature of 45°C, rotating the seed crystal rod at a speed of 14 rpm to grow the crystal, maintaining the temperature for 3 days, then lowering the temperature to room temperature at a rate of 0.6°C / h, and then taking the crystal out of the solution to obtain a Rb3[CH3SO3][NO3]2 nonlinear optical crystal with a size of 14 mm x 13 mm x 10 mm.

[0052] Example 5

[0053] The nonlinear optical crystal (NH4)3[CH3SO3][NO3]2 was synthesized by top-seeding method according to the reaction formula: 2NH4NO3+NH4CH3SO3→(NH4)3[CH3SO3][NO3]2.

[0054] (NH4)2CO3, methane sulfonic acid and NH4NO3 were directly mixed uniformly according to a molar ratio of 1:2:4 to obtain a mixture, and 50 ml of deionized water was added to fully dissolve the mixture to obtain a mixed solution; wherein the ammonium carbonate can be replaced by ammonium bicarbonate or ammonia water.

[0055] Preparation of compound (NH4)3[CH3SO3][NO3]2 seed crystal: the obtained mixed solution was kept at a constant temperature for 2 days, and was placed in a polytetrafluoroethylene beaker, and then was sealed with a polyvinyl chloride film, and was placed in a static environment without shaking, pollution and air convection, and a plurality of small holes were made on the seal to adjust the evaporation rate of the solvent in the solution. After the solution was saturated, crystals began to precipitate, and the better quality crystals were taken out to obtain the compound (NH4)3[CH3SO3][NO3]2 seed crystal.

[0056] The obtained seed crystal was fixed on a seed crystal rod, and the seed crystal was lowered to contact the surface of the prepared saturated mixed solution from the top of the aqueous solution crystal growth furnace. The temperature of the mixed solution was heated to 46°C, and the seed crystal rod was rotated at a speed of 20 rpm for crystal growth. After being kept at a constant temperature for 3 days, the crystal was taken out from the solution after the temperature was reduced to room temperature at a rate of 0.9°C / h, and a nonlinear optical crystal (NH4)3[CH3SO3][NO3]2 with a size of 13 mm x 11 mm x 11 mm was obtained.

[0057] Example 6

[0058] The nonlinear optical crystal K3[CH3SO3][NO3]2 was synthesized by top-seeding method according to the reaction formula: 2KNO3+KCH3SO3→K3[CH3SO3][NO3]2.

[0059] K2CO3, methane sulfonic acid and KNO3 were directly mixed uniformly according to a molar ratio of 1:2.2:4 to obtain a mixture, and 40 ml of deionized water was added to fully dissolve the mixture to obtain a mixed solution; wherein the potassium carbonate can be replaced by potassium bicarbonate or potassium hydroxide.

[0060] Preparation of compound K3[CH3SO3][NO3]2 seed crystal: the obtained mixed solution is kept constant temperature for 3 days, and is placed in a polytetrafluoroethylene beaker, and is sealed with a polyvinyl chloride film, and is placed in a static environment without shaking, pollution and air convection, a plurality of small holes are punched on the sealing to adjust the volatilization rate of the solvent in the solution, and the crystal is precipitated after the solution is saturated, and the crystal with good quality is taken out to be the compound K3[CH3SO3][NO3]2 seed crystal;

[0061] The obtained seed crystal is fixed on a seed crystal rod, the seed crystal is lowered from the top of the aqueous solution crystal growth furnace to contact the surface of the prepared saturated mixed solution, the temperature of the mixed solution is heated to 48 DEG C, the seed crystal rod is rotated at a speed of 23 rpm to grow the crystal, and the temperature is kept constant for 4 days, then the temperature is lowered to room temperature at a rate of 0.5 DEG C / h, and then the crystal is taken out from the solution to obtain a K3[CH3SO3][NO3]2 nonlinear optical crystal with a size of 26mm*12mm*18mm.

[0062] Example 7

[0063] According to the reaction formula: 2RbNO3+RbCH3SO3→Rb3[CH3SO3][NO3]2, Rb3[CH3SO3][NO3]2 nonlinear optical crystal is synthesized by using top seed crystal method:

[0064] Rb2CO3, methane sulfonic acid and RbNO3 are directly mixed uniformly according to a molar ratio of 1:2:3.8 to obtain a mixture, and 80ml of deionized water is added to fully dissolve the mixture to obtain a mixed solution; the rubidium carbonate can be replaced by rubidium bicarbonate and rubidium hydroxide;

[0065] Preparation of compound Rb3[CH3SO3][NO3]2 seed crystal: the obtained mixed solution is kept constant temperature for 3 days, and is placed in a polytetrafluoroethylene beaker, and is sealed with a polyvinyl chloride film, and is placed in a static environment without shaking, pollution and air convection, a plurality of small holes are punched on the sealing to adjust the volatilization rate of the solvent in the solution, and the crystal is precipitated after the solution is saturated, and the crystal with good quality is taken out to be the compound K3[CH3SO3][NO3]2 seed crystal;

[0066] The obtained seed crystal is fixed on a seed crystal rod, the seed crystal is lowered from the top of the aqueous solution crystal growth furnace to contact the surface of the prepared saturated mixed solution, the temperature of the mixed solution is heated to 48 DEG C, the seed crystal rod is rotated at a speed of 23 rpm to grow the crystal, and the temperature is kept constant for 4 days, then the temperature is lowered to room temperature at a rate of 0.5 DEG C / h, and then the crystal is taken out from the solution to obtain a K3[CH3SO3][NO3]2 nonlinear optical crystal with a size of 26mm*12mm*18mm.

[0067] Example 8

[0068] Cs3[CH3SO3][NO3]2 nonlinear optical crystal is synthesized by top seed method according to the reaction formula: 2CsNO3+CsCH3SO3→Cs3[CH3SO3][NO3]2:

[0069] Directly mix Cs2CO3, methane sulfonic acid and CsNO3 uniformly according to the molar ratio of 0.9:2:4 to obtain a mixture, and add 30 ml of deionized water to fully dissolve the mixture to obtain a mixed solution; wherein the cesium carbonate can be replaced by cesium bicarbonate and cesium hydroxide;

[0070] Preparation of compound Cs3[CH3SO3][NO3]2 seed crystal: the obtained mixed solution is kept at constant temperature for 2 days, and is placed in a polytetrafluoroethylene beaker, and then is sealed with a polyvinyl chloride film, and is placed in a static environment without shaking, pollution and air convection, a plurality of small holes are made on the sealing to adjust the evaporation rate of the solvent in the solution, and after the solution is saturated, the crystal is precipitated, and the crystal with good quality is taken out to obtain the compound Cs3[CH3SO3][NO3]2 seed crystal;

[0071] The obtained seed crystal is fixed on a seed crystal rod, the seed crystal is lowered from the top of the aqueous solution crystal growth furnace to contact the surface of the prepared saturated mixed solution, the temperature of the mixed solution is heated to 45°C, the seed crystal rod is rotated at a speed of 22 rpm for crystal growth, and the temperature is kept constant for 2 days, then the temperature is lowered to room temperature at a rate of 0.6°C / h, and then the crystal is taken out from the solution to obtain a Cs3[CH3SO3][NO3]2 nonlinear optical crystal with a size of 24 mm x 13 mm x 12 mm.

[0072] Example 9

[0073] (NH4)3[CH3SO3][NO3]2 nonlinear optical crystal is synthesized by top seed method according to the reaction formula: 2NH4NO3+NH4CH3SO3→(NH4)3[CH3SO3][NO3]2:

[0074] a. Mix NH4HCO3 and methane sulfonic acid uniformly according to the molar ratio of 1:1 to obtain a mixture, and add 20 ml of deionized water to fully dissolve the mixture to obtain a mixed solution; wherein ammonium bicarbonate can be replaced by ammonium carbonate and ammonia;

[0075] b. The mixed solution in step a is kept at constant temperature for 4 days, and the solvent is evaporated to supersaturation to precipitate the crystal, and the crystal is taken out when the solvent has not completely evaporated, and is placed on filter paper to dry, to obtain a methane sulfonic acid compound NH4CH3SO3;

[0076] c. Mix and grind NH4CH3SO3 obtained in step b and NH4NO3 uniformly according to the molar ratio of 1:2, and add 50 mL of deionized water to fully mix and dissolve, to obtain a mixed solution;

[0077] d. Preparation of compound (NH4)3[CH3SO3][NO3]2 seed crystal: the mixed solution in step c is kept constant for 2 days, and is placed in a polytetrafluoroethylene beaker, and is sealed with a polyvinyl chloride film, and is placed in a static environment without shaking, pollution and air convection, a plurality of small holes are punched on the seal to adjust the evaporation rate of the solvent in the solution, and when the solution is saturated, crystals begin to precipitate, and the better quality crystals are taken out as the compound (NH4)3[CH3SO3][NO3]2 seed crystal;

[0078] e. The seed crystal obtained in step d is fixed on the seed crystal rod, the seed crystal is lowered from the top of the aqueous solution crystal growth furnace to contact the surface of the saturated mixed solution prepared in step d, the temperature of the mixed solution is heated to 49°C, the seed crystal rod is rotated at a speed of 26 rpm for crystal growth, and the temperature is kept constant for 3 days, and then the temperature is lowered to room temperature at a rate of 1.3°C / h, and then the crystals are taken out from the solution, and a 12mm×8mm×6mm (NH4)3[CH3SO3][NO3]2 nonlinear optical crystal is obtained.

[0079] Example 10

[0080] According to the reaction formula: 2KNO3+KCH3SO3→K3[CH3SO3][NO3]2, K3[CH3SO3][NO3]2 nonlinear optical crystal is synthesized by top seed method:

[0081] a. KHCO3 and methane sulfonic acid are mixed uniformly in a molar ratio of 1:1.2 to obtain a mixture, and 90 ml of deionized water is added to fully dissolve the mixture to obtain a mixed solution; wherein the potassium bicarbonate can be replaced by potassium carbonate or potassium hydroxide;

[0082] b. The mixed solution in step a is kept constant for 3 days, and the solvent is evaporated to supersaturation to start precipitating crystals, and the crystals are taken out when the solvent has not completely evaporated, and are placed on filter paper to dry, to obtain a methane sulfonic acid compound KCH3SO3;

[0083] c. KCH3SO3 obtained in step b is mixed with KNO3 in a molar ratio of 1:2.2 and ground uniformly, and 40 mL of deionized water is added to fully mix and dissolve, to obtain a mixed solution;

[0084] d. Preparation of compound K3[CH3SO3][NO3]2 seed crystal: the mixed solution in step c is kept constant for 2 days, and is placed in a polytetrafluoroethylene beaker, and is sealed with a polyvinyl chloride film, and is placed in a static environment without shaking, pollution and air convection, a plurality of small holes are punched on the seal to adjust the evaporation rate of the solvent in the solution, and when the solution is saturated, crystals begin to precipitate, and the better quality crystals are taken out as the compound K3[CH3SO3][NO3]2 seed crystal;

[0085] e. Fix the seed crystal obtained in step d onto the seed crystal rod, lower the seed crystal from the top of the aqueous crystal growth furnace, and lower the seed crystal to the surface of the saturated mixed solution prepared in step d. Heat the mixed solution to 49°C, rotate the seed crystal rod at 16 rpm to grow the crystal, keep the temperature constant for 5 days, and then cool it to room temperature at a cooling rate of 1.2°C / h. After that, take the crystal out of the solution to obtain a 19mm×14mm×9mm K3[CH3SO3][NO3]2 nonlinear optical crystal.

[0086] Example 11

[0087] Based on the reaction formula: 2RbNO3 + KCH3SO3 → Rb3[CH3SO3][NO3]2, the Rb3[CH3SO3][NO3]2 nonlinear optical crystal was synthesized using the top-seeded crystal method.

[0088] a. Mix RbHCO3 and methanesulfonic acid at a molar ratio of 1:1.1 until homogeneous to obtain a mixture. Add 60 ml of deionized water to fully dissolve the mixture to obtain a solution. Rubidium bicarbonate can be replaced by rubidium carbonate or rubidium hydroxide.

[0089] b. Let the mixed solution in step a stand at a constant temperature for 2 days until the solvent evaporates to supersaturation and crystals begin to precipitate. Before the solvent has completely evaporated, take out the crystals and place them on filter paper to dry, to obtain the methanesulfonic acid compound RbCH3SO3.

[0090] c. Mix the RbCH3SO3 and RbNO3 obtained in step b at a molar ratio of 1:2.1 and grind them evenly. Add 40 mL of deionized water to mix and dissolve them thoroughly to obtain a mixed solution.

[0091] d. Preparation of Rb3[CH3SO3][NO3]2 seed crystals: The mixed solution in step c is kept at a constant temperature for 3 days, placed in a polytetrafluoroethylene beaker, 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 evaporation rate of the solvent in the solution. After the solution is saturated, crystals begin to precipitate. The better quality crystals are taken out as Rb3[CH3SO3][NO3]2 seed crystals.

[0092] e. Fix the seed crystal obtained in step d onto the seed crystal rod, lower the seed crystal from the top of the aqueous crystal growth furnace, and lower the seed crystal to the surface of the saturated mixed solution prepared in step d. Heat the mixed solution to 45°C, rotate the seed crystal rod at 25 rpm to grow the crystal, keep the temperature constant for 3 days, and then cool it to room temperature at a rate of 1.2°C / h. After that, take the crystal out of the solution to obtain a 15mm×14mm×12mm Rb3[CH3SO3][NO3]2 nonlinear optical crystal.

[0093] Example 12

[0094] The Cs3[CH3SO3][NO3]2 nonlinear optical crystal is synthesized by using the top seed method according to the reaction formula: 2CsNO3+CsCH3SO3→Cs3[CH3SO3][NO3]2.

[0095] a. The CsHCO3 and methane sulfonic acid are mixed uniformly in a molar ratio of 1:1 to obtain a mixture, and 20 ml of deionized water is added to fully dissolve the mixture to obtain a mixed solution; wherein the cesium bicarbonate can be replaced by cesium carbonate or cesium hydroxide;

[0096] b. The mixed solution in step a is placed at a constant temperature for 2 days, and the crystals are taken out when the solvent is not completely volatilized and placed on filter paper to dry, to obtain the methane sulfonic acid compound CsCH3SO3.

[0097] c. The CsCH3SO3 and CsNO3 obtained in step b are mixed and ground uniformly in a molar ratio of 1:2, and 20 ml of deionized water is added to fully mix and dissolve the mixture to obtain a mixed solution.

[0098] d. The compound Cs3[CH3SO3][NO3]2 seed crystal is prepared: the mixed solution in step c is placed at a constant temperature for 2 days in a polytetrafluoroethylene beaker, and then sealed with a polyvinyl chloride film, and placed in a static environment without shaking, pollution, and air convection. A few small holes are made on the seal to adjust the volatilization rate of the solvent in the solution. When the solution is saturated, crystals begin to precipitate, and the better quality crystals are taken out as the compound Cs3[CH3SO3][NO3]2 seed crystal.

[0099] e. The seed crystal obtained in step d is fixed on the seed crystal rod, and the seed crystal is lowered from the top of the aqueous solution crystal growth furnace to contact the surface of the saturated mixed solution prepared in step d. The temperature of the mixed solution is heated to 48°C, and the seed crystal rod is rotated at a speed of 19 rpm to grow the crystal. After being kept at a constant temperature for 4 days, the temperature is lowered to room temperature at a rate of 0.8°C / h. The crystal is taken out from the solution to obtain a Cs3[CH3SO3][NO3]2 nonlinear optical crystal with a size of 18 mm x 19 mm x 16 mm.

[0100] Example 13

[0101] The (NH4)3[CH3SO3]Cl2 nonlinear optical crystal is synthesized by using the top seed method according to the reaction formula: 2NH4Cl+NH4CH3SO3→(NH4)3[CH3SO3]Cl2.

[0102] NH4HCO3, methane sulfonic acid and NH4Cl are directly mixed uniformly in a molar ratio of 1:1.2:2 to obtain a mixture, and 50 ml of deionized water is added to fully dissolve the mixture to obtain a mixed solution; wherein the ammonium bicarbonate can be replaced by ammonium carbonate or ammonia water;

[0103] Preparation of compound (NH4)3[CH3SO3]Cl2 seed crystal: the obtained mixed solution is kept at a constant temperature for 5 days, and is placed in a polytetrafluoroethylene beaker, and then is sealed with a polyvinyl chloride film, and is placed in a static environment without shaking, pollution and air convection, a plurality of small holes are punched on the sealing to adjust the evaporation rate of the solvent in the solution, and after the solution is saturated, crystals begin to precipitate, and the better quality crystals are taken out to obtain the compound (NH4)3[CH3SO3]Cl2 seed crystal;

[0104] The obtained seed crystal is fixed on a seed crystal rod, the seed crystal is lowered from the top of the aqueous solution crystal growth furnace to contact the surface of the prepared saturated mixed solution, the temperature of the mixed solution is heated to 45℃, the seed crystal rod is rotated at a speed of 20 rpm to grow crystals, and the temperature is kept constant for 4 days, and then the temperature is lowered to room temperature at a rate of 0.8℃ / h, and then the crystals are taken out from the solution to obtain a (NH4)3[CH3SO3]Cl2 nonlinear optical crystal with a size of 42mm×28mm×10mm.

[0105] Example 14

[0106] According to the reaction formula: 2KCl+KCH3SO3→K3[CH3SO3]Cl2, K3[CH3SO3][NO3]2 nonlinear optical crystal is synthesized by using top seed crystal method:

[0107] KHCO3, methane sulfonic acid and KCl are directly mixed uniformly in a molar ratio of 1:1:2 to obtain a mixture, and 40 ml of deionized water is added to fully dissolve the mixture to obtain a mixed solution; wherein the potassium bicarbonate can be replaced by potassium carbonate or potassium hydroxide;

[0108] Preparation of compound K3[CH3SO3]Cl2 seed crystal: the obtained mixed solution is kept at a constant temperature for 3 days, and is placed in a polytetrafluoroethylene beaker, and then is sealed with a polyvinyl chloride film, and is placed in a static environment without shaking, pollution and air convection, a plurality of small holes are punched on the sealing to adjust the evaporation rate of the solvent in the solution, and after the solution is saturated, crystals begin to precipitate, and the better quality crystals are taken out to obtain the compound K3[CH3SO3]Cl2 seed crystal;

[0109] The obtained seed crystal is fixed on a seed crystal rod, the seed crystal is lowered to contact the surface of the prepared saturated mixed solution from the top of the aqueous solution crystal growth furnace, the temperature of the mixed solution is heated to 48°C, the crystal growth is carried out by rotating the seed crystal rod at a speed of 36 rpm, constant temperature is maintained for 4 days, then the temperature is lowered to room temperature at a rate of 2.8°C / h, then the crystal is taken out from the solution, and a K3[CH3SO3]Cl2 nonlinear optical crystal with a size of 22 mm x 11 mm x 4 mm is obtained.

[0110] Example 15

[0111] Rb3[CH3SO3]Cl2 nonlinear optical crystal is synthesized by using top seed crystal method according to the reaction formula: 2RbCl + RbCH3SO3→ Rb3[CH3SO3]Cl2.

[0112] RbHCO3, methane sulfonic acid and RbCl are directly mixed uniformly according to a molar ratio of 1.1:1.4:2.2 to obtain a mixture, 40 ml of deionized water is added to fully dissolve the mixture to obtain a mixed solution; wherein the rubidium bicarbonate can be replaced by rubidium carbonate or rubidium hydroxide;

[0113] Preparation of compound Rb3[CH3SO3]Cl2 seed crystal: the obtained mixed solution is kept at constant temperature for 5 days, and is placed in a polytetrafluoroethylene beaker, then is sealed with a polyvinyl chloride film, and is placed in a static environment without shaking, pollution and air convection, a plurality of small holes are punched on the sealing to adjust the evaporation rate of the solvent in the solution, and after the solution is saturated, crystals begin to precipitate, and the better crystals are taken out to obtain the compound Rb3[CH3SO3]Cl2 seed crystal;

[0114] The obtained seed crystal is fixed on a seed crystal rod, the seed crystal is lowered to contact the surface of the prepared saturated mixed solution from the top of the aqueous solution crystal growth furnace, the temperature of the mixed solution is heated to 48°C, the crystal growth is carried out by rotating the seed crystal rod at a speed of 36 rpm, constant temperature is maintained for 4 days, then the temperature is lowered to room temperature at a rate of 2.8°C / h, then the crystal is taken out from the solution, and a K3[CH3SO3]Cl2 nonlinear optical crystal with a size of 22 mm x 11 mm x 4 mm is obtained.

[0115] Example 16

[0116] Cs3[CH3SO3]Cl2 nonlinear optical crystal is synthesized by using top seed crystal method according to the reaction formula: 2CsCl + CsCH3SO3→ Cs3[CH3SO3]Cl2.

[0117] CsHCO3, methane sulfonic acid and CsCl are directly mixed uniformly according to a molar ratio of 1:1:2.2 to obtain a mixture, 60 ml of deionized water is added to fully dissolve the mixture to obtain a mixed solution; wherein the cesium bicarbonate can be replaced by cesium carbonate or cesium hydroxide;

[0118] Preparation of compound Cs3[CH3SO3]Cl2 seed crystal: the obtained mixed solution is kept constant temperature for 2 days, and is placed in a polytetrafluoroethylene beaker, and is sealed with a polyvinyl chloride film, and is placed in a static environment without shaking, pollution and air convection, a plurality of small holes are punched on the seal to adjust the volatilization rate of the solvent in the solution, and when the solution is saturated, crystals begin to precipitate, and the crystals with better quality are taken out as the compound Cs3[CH3SO3]Cl2 seed crystal;

[0119] The obtained seed crystal is fixed on a seed crystal rod, the seed crystal is lowered from the top of the aqueous solution crystal growth furnace to contact the surface of the prepared saturated mixed solution, the temperature of the mixed solution is heated to 50 DEG C, the seed crystal rod is rotated at a speed of 9 rpm for crystal growth, and the temperature is kept constant for 5 days, and then the temperature is lowered to room temperature at a rate of 1.8 DEG C / h, and then the crystals are taken out from the solution, and a 32mm x 20mm x 18mm Cs3[CH3SO3]Cl2 nonlinear optical crystal is obtained.

[0120] Example 17

[0121] According to the reaction formula: 2NH4Br+NH4CH3SO3→(NH4)3[CH3SO3]Br2, a top seed crystal method is used to synthesize a (NH4)3[CH3SO3]Br2 nonlinear optical crystal:

[0122] NH4HCO3, methane sulfonic acid and NH4Br are directly mixed uniformly in a molar ratio of 1:1.2:2 to obtain a mixture, and 50 ml of deionized water is added to fully dissolve the mixture to obtain a mixed solution; wherein the ammonium bicarbonate can be replaced by ammonium carbonate and ammonia water;

[0123] Preparation of compound (NH4)3[CH3SO3]Br2 seed crystal: the obtained mixed solution is kept constant temperature for 3 days, and is placed in a polytetrafluoroethylene beaker, and is sealed with a polyvinyl chloride film, and is placed in a static environment without shaking, pollution and air convection, a plurality of small holes are punched on the seal to adjust the volatilization rate of the solvent in the solution, and when the solution is saturated, crystals begin to precipitate, and the crystals with better quality are taken out as the compound (NH4)3[CH3SO3]Br2 seed crystal;

[0124] The obtained seed crystal is fixed on a seed crystal rod, the seed crystal is lowered from the top of the aqueous solution crystal growth furnace to contact the surface of the prepared saturated mixed solution, the temperature of the mixed solution is heated to 46 DEG C, the seed crystal rod is rotated at a speed of 14 rpm for crystal growth, and the temperature is kept constant for 2 days, and then the temperature is lowered to room temperature at a rate of 0.8 DEG C / h, and then the crystals are taken out from the solution, and a 15mm x 14mm x 11mm (NH4)3[CH3SO3]Br2 nonlinear optical crystal is obtained.

[0125] Example 18

[0126] K3[CH3SO3]Br2 nonlinear optical crystal is synthesized by top-seed method according to the reaction formula: 2KNO3+KCH3SO3→K3[CH3SO3]Br2:

[0127] KHCO3, methane sulfonic acid and KBr are directly mixed uniformly according to the molar ratio of 0.7:0.9:2.2 to obtain a mixture, and 90 ml of deionized water is added to fully dissolve the mixture to obtain a mixed solution; wherein the potassium bicarbonate can be replaced by potassium carbonate or potassium hydroxide;

[0128] Preparation of compound K3[CH3SO3]Br2 seed crystal: the obtained mixed solution is kept at a constant temperature for 3 days, and is placed in a polytetrafluoroethylene beaker, and then is sealed with a polyvinyl chloride film, and is placed in a static environment without shaking, pollution and air convection, a plurality of small holes are punched on the seal to adjust the evaporation rate of the solvent in the solution, and after the solution is saturated, the crystal starts to precipitate, and the crystal with better quality is taken out as the compound K3[CH3SO3]Br2 seed crystal;

[0129] The obtained seed crystal is fixed on a seed crystal rod, the seed crystal is lowered to the surface of the prepared saturated mixed solution from the top of the aqueous solution crystal growth furnace, the temperature of the mixed solution is heated to 50°C, the seed crystal rod is rotated at a speed of 11 rpm to grow the crystal, and the temperature is kept constant for 5 days, then the temperature is lowered to room temperature at a rate of 0.8°C / h, and then the crystal is taken out from the solution, thereby obtaining a K3[CH3SO3]Br2 nonlinear optical crystal with a size of 13 mm x 10 mm x 9 mm.

[0130] Example 19

[0131] Rb3[CH3SO3]Br2 nonlinear optical crystal is synthesized by top-seed method according to the reaction formula: 2RbNO3+RbCH3SO3→K3[CH3SO3]Br2:

[0132] RbHCO3, methane sulfonic acid and RbBr are directly mixed uniformly according to the molar ratio of 1.2:1:2.1 to obtain a mixture, and 70 ml of deionized water is added to fully dissolve the mixture to obtain a mixed solution; wherein the rubidium bicarbonate can be replaced by rubidium carbonate or rubidium hydroxide;

[0133] Preparation of compound Rb3[CH3SO3]Br2 seed crystal: the obtained mixed solution is kept at a constant temperature for 5 days, and is placed in a polytetrafluoroethylene beaker, and then is sealed with a polyvinyl chloride film, and is placed in a static environment without shaking, pollution and air convection, a plurality of small holes are punched on the seal to adjust the evaporation rate of the solvent in the solution, and after the solution is saturated, the crystal starts to precipitate, and the crystal with better quality is taken out as the compound Rb3[CH3SO3][NO3]2 seed crystal;

[0134] The obtained seed crystal is fixed on a seed crystal rod, the seed crystal is lowered from the top of the water solution crystal growth furnace to contact the surface of the prepared saturated mixed solution, the temperature of the mixed solution is heated to 50°C, the crystal growth is carried out by rotating the seed crystal rod at a speed of 11 rpm, the temperature is kept constant for 5 days, then the temperature is lowered to room temperature at a rate of 0.9°C / h, then the crystal is taken out from the solution, and thus a Rb3[CH3SO3]Br2 nonlinear optical crystal with a size of 16 mm x 13 mm x 7 mm is obtained.

[0135] Example 20

[0136] A Cs3[CH3SO3]Br2 nonlinear optical crystal is synthesized by using a top seed crystal method according to the following reaction formula: 2CsNO3+CsCH3SO3→Cs3[CH3SO3]Br2.

[0137] CsHCO3, methane sulfonic acid and CsBr are directly mixed uniformly according to a molar ratio of 1.1:1:2.4 to obtain a mixture, and 80 ml of deionized water is added to fully dissolve the mixture to obtain a mixed solution; wherein the cesium bicarbonate can be replaced by cesium carbonate or cesium hydroxide.

[0138] Preparation of a compound Cs3[CH3SO3]Br2 seed crystal: the obtained mixed solution is kept constant at a temperature for 3 days, is placed in a polytetrafluoroethylene beaker, is sealed with a polyvinyl chloride film, is placed in a static environment without shaking, pollution and air convection, a plurality of small holes are punched on the sealing to adjust the evaporation rate of the solvent in the solution, and the crystal is precipitated after the solution is saturated, and the crystal with good quality is taken out to obtain the compound Cs3[CH3SO3]Br2 seed crystal.

[0139] The obtained seed crystal is fixed on a seed crystal rod, the seed crystal is lowered from the top of the water solution crystal growth furnace to contact the surface of the prepared saturated mixed solution, the temperature of the mixed solution is heated to 45°C, the crystal growth is carried out by rotating the seed crystal rod at a speed of 10 rpm, the temperature is kept constant for 5 days, then the temperature is lowered to room temperature at a rate of 0.8°C / h, then the crystal is taken out from the solution, and thus a Cs3[CH3SO3]Br2 nonlinear optical crystal with a size of 20 mm x 15 mm x 10 mm is obtained.

[0140] Example 21

[0141] Any A3[CH3SO3]X2 nonlinear optical crystal obtained in Examples 1-20 is processed according to a matching direction, is arranged at a position of 3 according to the arrangement shown in FIG. 3, and is used as a light source at room temperature. Figure 3 An infrared light beam 2 with a wavelength of 1064 nm emitted by a Q-switched Nd:YAG laser 1 is incident on the A3[CH3SO3]X2 single crystal 3, green frequency-doubled light with a wavelength of 532 nm is generated, and the output intensity is about 1.0-1.4 times that of KDP under the same conditions.

Claims

1. A series of compound methane sulfonate nonlinear optical crystals, characterized in that... The general molecular formula of this crystal is A3[CH3SO3]X2, where A = NH4, K, Rb, Cs, and X = [NO3], Cl, Br. It does not have a center of symmetry, belongs to the orthorhombic crystal system, and has a space group of [missing information]. Cmc 21 (No. 36), cell parameters: 1) (NH4)3[CH3SO3][NO3]2: a = 12.0478(14) Å, b = 8.0546(12)Å, c = 10.9667(9) Å, α=90, β=90, γ=90, Z = 4, V= 1063.0(2)Å 3 ; 2) K3[CH3SO3][NO3]2: a =12.2145(1) Å, b = 8.1351(1) Å, c = 10.9954(14) Å, α=90, β=90, γ=90, Z = 4, V=1087.0(2)Å 3 ; 3) Rb3[CH3SO3][NO3]2: a = 12.3161(10) Å, b = 8.3512(10) Å, c = 11.2211(2) Å, α=90, β=90, γ=90, Z = 4, V= 1135.27 (4)Å 3 ; 4) Cs3[CH3SO3][NO3]2: a = 12.210(4)Å, b = 8.417(4) Å, c = 11.5247(8) Å, α=90, β=90, γ=90, Z = 4, V= 1552.35(1) Å 3 ; 5) (NH4)3[CH3SO3]Cl2: a = 12.4124(14) Å, b = 8.3304(12) Å, c = 11.2233(9) Å, α=90, β=90, γ=90, Z = 4, V= 1158.93(6)Å 3 ; 6) K3[CH3SO3]Cl2: a = 12.0047(14) Å, b = 8.2555(12) Å, c = 10.9898(9) Å, α=90, β=90, γ=90, Z = 4, V= 1087.9(9)Å 3 ; 7) Rb3[CH3SO3]Cl2: a = 12.4265(15) Å, b = 8.3310(12) Å, c = 11.4513 (9) Å, α=90, β=90, γ=90, Z = 4, V=1185.3(6)Å 3 ; 8)Cs3[CH3SO3]Cl2: a = 12.5667(15) Å, b = 8.4995(1) Å, c = 11.3622(15) Å, α = 90, β = 90, γ = 90, Z = 4, V = 1212.8(2) Å 3 ; 9) (NH4)3[CH3SO3]Br2:a = 12.4415(14) Å,b = 8.3257(2) Å,c = 11.3254 (9) Å,α=90,β=90,γ=90,Z = 4,V= 1172.3(3)Å 3 ; 10) K3[CH3SO3]Br2: a = 12.5455(6) Å, b = 8.1453(17) Å, c = 11.0047(9) Å, α=90, β=90, γ=90, Z = 4, V= 1122.8(3) Å 3 ;11) Rb3[CH3SO3]Br2:a = 12.2773(6) Å,b = 8.4044(17) Å,c= 11.2245 (9) Å,α=90,β=90,γ=90,Z = 4,V= 1156.4(2)Å 3 ; 12) Cs3[CH3SO3]Br2:a =12.4258(2) Å,b = 8.4145(4) Å,c = 11.3878(15) Å,α=90,β=90,γ=90,Z = 4,V=1187.8(7)Å 3 。 2. The method for preparing a series of methane sulfonate nonlinear optical crystals according to claim 1, characterized in that... The top-seeded method is used for preparation, and the specific operation is carried out according to the following steps: a. Mix a compound containing ammonium, potassium, rubidium, or cesium with methanesulfonic acid at a molar ratio of 1:1-2 until homogeneous, add 0-50 mL of deionized water to fully mix and dissolve, and obtain a mixture. The compound containing ammonium, potassium, rubidium, or cesium is ammonium carbonate, potassium carbonate, rubidium carbonate, cesium carbonate, ammonium bicarbonate, potassium bicarbonate, rubidium bicarbonate, cesium bicarbonate, ammonia, potassium hydroxide, rubidium hydroxide, or cesium hydroxide. b. Keep the mixed solution in step a at a constant temperature for 2-5 days until the solvent evaporates to supersaturation and crystals begin to precipitate. Before the solvent has completely evaporated, take out the crystals and place them on filter paper to dry, to obtain a series of methanesulfonate ammonium, methanesulfonate potassium, methanesulfonate rubidium or methanesulfonate containing methanesulfonate compounds. c. Mix the methanesulfonic acid compound from step b with the nitric acid or halogen compound at a molar ratio of 1:2 and grind them evenly. Add 50-150 mL of deionized water to fully mix and dissolve the mixture to obtain a solution containing ammonium nitrate, potassium nitrate, rubidium nitrate, cesium nitrate, ammonium chloride, potassium chloride, rubidium chloride, cesium chloride, ammonium bromide, potassium bromide, rubidium bromide, or cesium bromide. Alternatively, directly mix compounds containing ammonium, potassium, rubidium, or cesium, methanesulfonic acid, and compounds containing nitric acid or halogens in a molar ratio of 0.7-1.2:0.9-2.2:2-4 to obtain a homogeneous mixture, then add 30-90 ml of deionized water to fully dissolve the mixture to obtain a solution. d. Preparation of the A3[CH3SO3]X2 seed crystals: The mixed solution in step c is kept at a constant temperature for 2-5 days in a polytetrafluoroethylene beaker, 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 evaporation rate of the solvent in the solution. After the solution is saturated, crystals begin to precipitate. The crystals with better quality are taken out, which are the A3[CH3SO3]X2 seed crystals. e. Fix the seed crystal obtained in step d onto the seed crystal rod, lower the seed crystal from the top of the aqueous crystal growth furnace, and place the seed crystal on the surface of the saturated mixed solution in contact with the solution obtained in step d. Heat the mixed solution to 40-60℃, rotate the seed crystal rod at 5-60 rpm to grow the crystal, keep the temperature constant for 1-3 days, and then cool it down to room temperature at a rate of 0.5℃ / h. Remove the crystal from the solution to obtain the nonlinear optical crystal of the series of compounds A3[CH3SO3]X2.

3. The use of the series of compound methane sulfonate nonlinear optical crystals according to claim 1 in preparing second-harmonic light output from the 1064 nm fundamental frequency light output by an Nd:YAG laser.

Images