A nonlinear optical crystal barium methylsulfonate and a preparation method and use thereof

Abstract

The application relates to a novel optoelectronic functional material and a growth method and use, in particular to a nonlinear optical crystal barium methylsulfonate and a preparation method and use thereof, the chemical formula of the barium methylsulfonate crystal is Ba(SO3CH3)2, the barium methylsulfonate crystal is a nonlinear optical crystal, the crystal is an orthorhombic system, the space group is Cmc21, and the cell parameter is alpha = beta = gamma = 90 DEG. The powder frequency doubling effect of the barium methylsulfonate crystal is 1.2 times that of KH2PO4 (KDP). It is shown that the barium methylsulfonate nonlinear optical crystal has good phase matching capability.

Description

Technical Field

[0001] This invention relates to a novel optoelectronic functional material, its growth method, and its applications, particularly to a nonlinear optical crystal, barium methanesulfonate, its preparation method, and its applications. Background Technology

[0002] With the development of 193nm photolithography technology and micro and nano-precision laser processing, modern instruments such as ultra-high energy resolution photoelectron spectrometers and photoelectron emission microscopy (PEEM), as well as basic research such as chemical reaction kinetics, have created a strong and urgent demand for deep ultraviolet laser sources / coherent light sources (generally referring to wavelengths shorter than 200nm). At present, all-solid-state deep ultraviolet laser sources have become a research hotspot in the international laser science community in recent years.

[0003] Currently, although both synchrotron radiation sources and excimer lasers can generate deep ultraviolet coherent light sources, synchrotron radiation sources are large in size and have poor beam monochromaticity, resulting in low efficiency in obtaining specific narrow band wavelengths. Excimer lasers, on the other hand, do not meet the requirements of ultra-high energy resolution photoelectron spectrometers and photoelectron emission microscopes in terms of beam linewidth and mode, and are also very inconvenient to operate. In other words, the current beams are not only of low quality but also have large linewidths.

[0004] Obtaining a deep-ultraviolet laser source with high beam quality and narrow linewidth, meaning high energy precision for each photon, is a crucial task facing the laser technology community. Since the mid-to-late 1990s, scientists have considered obtaining deep-ultraviolet coherent light sources with wavelengths below 200 nm as a significant barrier. This barrier arises because the laser matrix crystal is limited by the energy levels of activated ions, making it difficult to directly generate deep-ultraviolet lasers. To overcome this barrier, high-power visible and near-infrared all-solid-state lasers are used as the fundamental frequency source, and multi-level frequency conversion technology using nonlinear optical crystals is employed to develop all-solid-state deep-ultraviolet coherent light sources.

[0005] The key challenge in developing all-solid-state deep ultraviolet coherent light sources using multi-stage frequency conversion technology with nonlinear optical crystals lies in developing nonlinear optical crystals suitable for generating deep ultraviolet harmonic light output, especially those capable of generating deep ultraviolet coherent light sources using frequency doubling methods. Summary of the Invention

[0006] To address the aforementioned problems in the prior art, this invention provides a barium methanesulfonate crystal with the chemical formula Ba(SO3CH3)2. This crystal is a nonlinear optical crystal, belonging to an orthorhombic crystal system with space group Cmc21 and cell parameters of [missing information]. α = β = γ = 90°;

[0007] According to an embodiment of the present invention, the crystal has the following characteristics: Figure 1 The X-ray crystal diffraction pattern shown;

[0008] According to an embodiment of the present invention, the number of molecules in the unit cell of the crystal is Z = 4;

[0009] According to an embodiment of the present invention, the unit cell volume of the crystal is

[0010] According to an embodiment of the present invention, the powder frequency doubling effect of the crystal is 1.2 times that of KH2PO4 (KDP);

[0011] According to an embodiment of the present invention, the crystal is capable of achieving a second harmonic harmonic of Nd:YAG (λ=1.064μm);

[0012] According to an embodiment of the present invention, the ultraviolet absorption edge of the crystal is shorter than 200 nm, preferably shorter than 190 nm, and for example, 195 nm, 190 nm, or 185 nm;

[0013] According to an embodiment of the present invention, the crystal is a colorless and transparent crystal;

[0014] According to an embodiment of the present invention, the volume of the crystal is greater than 10.0 mm. 3 Preferably, it is greater than 11.0 mm. 3 For example, it is 11.0 mm. 3 11.5mm 3 .

[0015] The present invention also provides a method for preparing the above-mentioned barium methanesulfonate crystals, comprising recrystallizing a solution of barium methanesulfonate compound to obtain barium methanesulfonate crystals.

[0016] Preferably, the recrystallization is carried out by evaporation at a constant temperature of 50-80°C, preferably 55-65°C, and exemplaryly 55°C, 60°C, or 65°C.

[0017] Preferably, the evaporation time under constant temperature is 2-10 days, more preferably 3-7 days, with 3 days, 4 days, and 7 days being exemplary.

[0018] According to an embodiment of the present invention, before recrystallization, the container holding the barium methanesulfonate compound solution is sealed with a semi-permeable membrane, preferably, the semi-permeable membrane is a plastic wrap and / or filter paper.

[0019] The present invention also provides a method for preparing the above-mentioned barium methanesulfonate compound, which involves reacting BaCO3 and HSO3CH3 to obtain barium methanesulfonate.

[0020] Preferably, barium carbonate is first dispersed in a solvent, then methanesulfonic acid is added dropwise until the solution becomes transparent. The reaction vessel is then sealed, and the reaction is carried out at a temperature of 70-90°C to obtain a barium methanesulfonate compound solution.

[0021] According to an embodiment of the present invention, the molar ratio of BaCO3 and HSO3CH3 can be 1:(2-2.6), preferably 1:(2-2.3); exemplaryly, it can be 1:2, 1:2.2, or 1:2.6.

[0022] According to an embodiment of the present invention, the reaction is carried out in a solvent selected from organic or inorganic solvents, preferably inorganic solvents, such as water, exemplarily deionized water.

[0023] According to an embodiment of the present invention, the reaction temperature can be 80-90°C, and exemplarily, the reaction temperature is 70°C, 80°C, or 90°C.

[0024] As an example, first place barium carbonate in 200 ml of deionized water to form a suspension, then add 52.5 ml of methanesulfonic acid dropwise to the beaker until the system is clear and transparent; seal the beaker with plastic wrap and place it in an oven, first slowly heat the oven to 70°C to react and form a Ba(SO3CH3)2 solution, then slowly cool it to 55°C and evaporate it at a constant temperature for 3 days to obtain a Ba(SO3CH3)2 single crystal with a size of 6.5×4×2 mm.

[0025] As an example, first place barium carbonate in 400 ml of deionized water to form a suspension, then add 105 ml of methanesulfonic acid dropwise to the beaker until the system is clear and transparent; seal the beaker with plastic wrap and place it in an oven, first slowly heat the oven to 90℃ to react and form a Ba(SO3CH3)2 solution, then slowly cool it to 65℃ and evaporate it at a constant temperature for 7 days to obtain centimeter-sized Ba(SO3CH3)2 single crystals with a size of 2.2×1.6×0.8 cm.

[0026] According to an embodiment of the present invention, the preparation method further includes: after the reaction is completed, collecting the barium methanesulfonate compound from the reaction solution.

[0027] The present invention also provides the use of the above-mentioned barium methanesulfonate crystals in optical devices.

[0028] According to an embodiment of the present invention, the barium methanesulfonate crystal is used for frequency conversion of laser output, harmonic generator in the ultraviolet region, optical parameter and amplifier device, or optical waveguide device.

[0029] Preferably, the barium methanesulfonate crystal is used to generate harmonic light output at 2nd, 3rd, 4th, 5th, or 6th harmonics from a laser beam with a wavelength of 1.064 μm.

[0030] Preferably, the barium methanesulfonate crystal is used for optical parametric and amplification devices in the infrared to ultraviolet regions.

[0031] The present invention also provides an optical device comprising the above-mentioned barium methanesulfonate crystal.

[0032] According to an embodiment of the present invention, the optical device may be a laser, a harmonic generator, an optical parametric and amplification device, or an optical waveguide device; preferably a laser; more preferably, the laser is an all-solid-state laser.

[0033] For example, an all-solid-state laser contains the Ba(SO3CH3)2 crystal. Preferably, the all-solid-state laser is an all-solid-state deep ultraviolet laser.

[0034] Beneficial effects

[0035] (1) The barium methanesulfonate nonlinear optical crystal provided by the present invention has a powder frequency doubling effect that is 1.2 times that of KH2PO4 (KDP). This indicates that the barium methanesulfonate nonlinear optical crystal has good phase matching ability; at the same time, its ultraviolet absorption edge is shorter than 200nm, so the Ba(SO3CH3)2 nonlinear optical crystal can achieve the second harmonic of Nd:YAG (λ=1.064μm); and it can be predicted that the Sr(NH2SO3)2 crystal can be used for the third, fourth, fifth and sixth harmonic generators of Nd:YAG, and even for generating harmonic light output shorter than 200nm.

[0036] (2) The Ba(SO3CH3)2 single crystal prepared by this invention is colorless and transparent, does not deliquesce, and has good chemical stability. Therefore, it is expected to be widely used in various nonlinear optical fields and will open up the application of nonlinear optical crystal materials in the deep ultraviolet band, so as to promote the development of related disciplines and industrial technologies. Attached Figure Description

[0037] Figure 1 The X-ray powder diffraction pattern of the Ba(SO3CH3)2 single crystal obtained in Example 1 is shown.

[0038] Figure 2 This is a schematic diagram of the single-cell structure of Ba(SO3CH3)2 crystal.

[0039] Figure 3 This is a typical schematic diagram of the nonlinear optical effects of Ba(SO3CH3)2 crystal when it is used as a frequency doubling crystal.

[0040] In the figure: 1 is the laser, 2 is the incident laser beam, 3 is the single crystal of Example 2 after crystal post-processing and optical processing, 4 is the emitted laser beam, and 5 is the filter. Detailed Implementation

[0041] The following detailed description, in conjunction with specific embodiments, illustrates the general formula compounds of the present invention, their preparation methods, and applications in further detail. It should be understood that the following embodiments are merely illustrative and explanatory of the present invention and should not be construed as limiting the scope of protection of the present invention. All technologies implemented based on the above content of the present invention are covered within the scope of protection intended by the present invention.

[0042] Unless otherwise stated, the raw materials and reagents used in the following examples are commercially available products or can be prepared by known methods.

[0043] In the following examples, the obtained Ba(SO3CH3)2 single crystal was characterized by X-ray diffraction using a Rigaku Mini-flex 600 powder diffractometer equipped with a Cu target; test conditions: room temperature.

[0044] Example 1

[0045] Ba(SO3CH3)2 single crystals were prepared by isothermal evaporation reaction.

[0046] Raw material used to prepare Ba(SO3CH3)2 single crystal: 72.1 g (0.364 mol) of BaCO3.

[0047] HSO3CH3 47.3ml (0.728mol)

[0048] The specific operating steps are as follows: Weigh the raw materials according to the above dosage in the operating box. First, place the barium carbonate in 200ml of deionized water to form a suspension. Then, add 52.5ml of methanesulfonic acid dropwise to the beaker until the system is clear and transparent. Seal the beaker with polyvinylidene chloride (PVDC) plastic wrap and place it in an oven. First, slowly heat the oven to 70℃ to react and form a Ba(SO3CH3)2 solution. Then, slowly cool it to 55℃ and evaporate it at a constant temperature for 3 days to obtain a Ba(SO3CH3)2 single crystal with a size of 6.5×4×2mm.

[0049] The X-ray powder diffraction pattern of the Ba(SO3CH3)2 single crystal obtained in this embodiment is as follows: Figure 1 As shown in the figure, the results indicate that the Ba(SO3CH3)2 single crystal obtained in this embodiment is a single pure phase with high purity.

[0050] Its single-cell structure diagram is as follows Figure 2 As shown. The obtained Ba(SO3CH3)2 single crystal does not have a center of symmetry, belongs to the orthorhombic crystal system, has a space group of Cmc21, and a unit cell parameter of... α=β=γ=90°. Z=4; unit cell volume is

[0051] Example 2

[0052] Ba(SO3CH3)2 single crystals were prepared by isothermal evaporation reaction.

[0053] Raw material used to prepare Ba(SO3CH3)2 single crystal: 72.1 g (0.364 mol) of BaCO3.

[0054] HSO3CH3 52.5ml (0.808mol)

[0055] The specific operating steps are as follows: Weigh the raw materials according to the above dosage. First, place the barium carbonate in 200ml of deionized water to form a suspension. Then, add 52.5ml of methanesulfonic acid dropwise to the beaker until the system is clear and transparent. Seal the beaker with polyvinylidene chloride (PVDC) plastic wrap and place it in an oven. First, slowly heat the oven to 80℃ to react and form a Ba(SO3CH3)2 solution. Then, slowly cool it to 60℃ and evaporate it at a constant temperature for 4 days to obtain Ba(SO3CH3)2 single crystals with a size of 7×4.5×2mm.

[0056] Example 3

[0057] Ba(SO3CH3)2 single crystals were prepared by isothermal evaporation reaction.

[0058] Raw material used to prepare Ba(SO3CH3)2 single crystal: 144.2 g (0.728 mol) of BaCO3.

[0059] HSO3CH3 123ml (1.893mol)

[0060] The specific operating steps are as follows: Weigh the raw materials according to the above dosage. First, place barium carbonate in 400ml of deionized water to form a suspension. Then, add 105ml of methanesulfonic acid dropwise to the beaker until the system is clear and transparent. Seal the beaker with polyvinylidene chloride (PVDC) plastic wrap and place it in an oven. First, slowly heat the oven to 90℃ to react and form a Ba(SO3CH3)2 solution. Then, slowly cool it to 65℃ and evaporate it at a constant temperature for 7 days to obtain centimeter-sized Ba(SO3CH3)2 single crystals with a size of 2.2×1.6×0.8cm.

[0061] Test Example 1

[0062] A frequency doubling test was performed on the Ba(SO3CH3)2 crystal sample obtained in Example 2. The structure of the test device is as follows: Figure 3 As shown.

[0063] The Ba(SO3CH3)2 crystal obtained in Example 2 was processed, cut, oriented, polished, and then placed in... Figure 3 At position 3 in the device shown, at room temperature, a Q-switched Nd:YAG laser is used as the input light source for laser 1. The incident wavelength of the incident laser beam 2 is 1064 nm. After the incident laser beam 2 passes through the single crystal 3 of Example 2 (which undergoes crystal post-processing and optical fabrication), the output laser beam 4 is observed to be a distinct 532 nm frequency-doubled green light output after passing through the filter 5. The output intensity (powder frequency doubling effect) of Ba(SO3CH3)2 is approximately 1.2 times that of KDP under the same conditions.

[0064] Test Example 2

[0065] Unlike Example 3, frequency-doubled light from a Q-switched Nd:YAG laser was used as the input light source for laser 1. The incident wavelength of the incident laser beam 2 was 532nm. It was observed that the output laser beam 4, after passing through the filter 5, showed a clear 266nm frequency-doubled ultraviolet light output.

[0066] Test Example 3

[0067] Unlike Example 3, the third harmonic light of a Q-switched Nd:YAG laser was used as the input light source for laser 1, with an incident wavelength of 355nm, and 177.3nm harmonic deep ultraviolet light output could be observed.

[0068] The embodiments of the present invention have been described above. However, the present invention is not limited to the above embodiments. Any modifications, equivalent substitutions, improvements, etc., made within the spirit and principles of the present invention should be included within the protection scope of the present invention.

Claims

1. The use of a barium methanesulfonate crystal in optical devices; The chemical formula of the barium methanesulfonate crystal is Ba(SO3CH3)2. It is a nonlinear optical crystal with an orthorhombic crystal system, space group Cmc21, and cell parameters a=6.307(3) Å, b=16.621(10) Å, c=7.534(4) Å, α=β=γ=90°.

2. The use according to claim 1, characterized in that, The number of molecules in the unit cell of the crystal is Z = 4; The unit cell volume of the crystal is V = 789.78(70) Å. 3 ; The powder frequency doubling effect of the crystal is 1.2 times that of KH2PO4; The crystal is capable of achieving frequency doubling of Nd:YAG; The ultraviolet absorption edge of the crystal is shorter than 200 nm.

3. The use according to claim 1, characterized in that, The crystal is a colorless and transparent crystal; the volume of the crystal is greater than 10.0 mm. 3 .

4. The use according to claim 1, characterized in that, The method for preparing barium methanesulfonate crystals includes recrystallizing a solution of barium methanesulfonate compound to obtain barium methanesulfonate crystals.

5. The use according to claim 4, characterized in that, The recrystallization is carried out by evaporation at a constant temperature of 50-80°C. The evaporation time under constant temperature is 2-10 days.

6. The use according to claim 4, characterized in that, The barium methanesulfonate compound is prepared by reacting BaCO3 and HSO3CH3.

7. The use according to claim 6, characterized in that, The preparation method of the barium methanesulfonate compound includes: first dispersing barium carbonate in a solvent, then adding methanesulfonic acid dropwise until transparent, sealing the reaction vessel, and reacting at a temperature of 70-90℃ to obtain a barium methanesulfonate compound solution.

8. The use according to claim 7, characterized in that, The reaction temperature is 80-90℃, and the molar ratio of BaCO3 to HSO3CH3 is 1:(2-2.6).

9. The use according to claim 7, characterized in that, The reaction is carried out in a solvent, which is selected from organic or inorganic solvents.

10. The use according to claim 4, characterized in that, Before recrystallization, the process also includes sealing the container holding the barium methanesulfonate compound solution with a semi-permeable membrane, which is a plastic wrap and / or filter paper.

11. The use according to claim 4, characterized in that, First, place barium carbonate in 200ml of deionized water to form a suspension. Then, add 52.5ml of methanesulfonic acid dropwise to the beaker until the system is clear and transparent. Seal the beaker with plastic wrap and place it in an oven. First, slowly heat the oven to 70℃ to react and form a Ba(SO3CH3)2 solution. Then, slowly cool it to 55℃ and evaporate it at a constant temperature for 3 days to obtain a Ba(SO3CH3)2 single crystal with a size of 6.5×4×2mm.

12. The use according to claim 4, characterized in that, First, place barium carbonate in 400 ml of deionized water to form a suspension. Then, add 105 ml of methanesulfonic acid dropwise to the beaker until the system is clear and transparent. Seal the beaker with plastic wrap and place it in an oven. First, slowly heat the oven to 90°C to react and form a Ba(SO3CH3)2 solution. Then, slowly cool it to 65°C and evaporate it at a constant temperature for 7 days to obtain centimeter-sized Ba(SO3CH3)2 single crystals with a size of 2.2 × 1.6 × 0.8 cm.

13. The use according to claim 1, characterized in that, The barium methanesulfonate crystal is used for frequency conversion of laser output, harmonic generators in the ultraviolet region, optical parameter and amplifier devices, or optical waveguide devices.

14. The use according to claim 1, characterized in that, The barium methanesulfonate crystal is used to generate harmonic light output at 2nd, 3rd, 4th, 5th, or 6th harmonics from a laser beam with a wavelength of 1.064 μm.

15. The use according to claim 13, characterized in that, The barium methanesulfonate crystal is used for optical parametric and amplification devices in the infrared to ultraviolet regions.

16. The use according to claim 1, characterized in that, The optical device is a laser, a harmonic generator, an optical parametric amplifier, or an optical waveguide.

17. The use according to claim 16, characterized in that, The laser is an all-solid-state laser.

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