Magnesium malonate dihydrate compound, method for preparing and use of its nonlinear optical crystal

Abstract

The application relates to a preparation method and use of a magnesium malonate dihydrate compound and a nonlinear optical crystal thereof, the chemical formula of the magnesium malonate dihydrate compound is Mg(C3H2O4)2H2O, the magnesium malonate dihydrate compound is a nonlinear optical crystal, belongs to an orthorhombic system, the space group is Pca21, the cell parameter is alpha=gamma=beta=90 DEG, and Z=4; the nonlinear optical crystal has good phase matching capability; meanwhile, the ultraviolet absorption edge is 190 nm, so that the Mg(C3H2O4)2H2O nonlinear optical crystal can realize 2 times frequency doubling of Nd:YAG (lambda=1.064 mu m).

Description

Technical Field

[0001] This invention relates to a novel optoelectronic functional material, its preparation method, and its applications, particularly to a magnesium malonate dihydrate compound and its nonlinear optical crystal preparation method and applications. Background Technology

[0002] Solid-state lasers are devices that convert electrical energy into light energy, generating high-energy, high-precision, and low-noise pulsed or continuous beams. Because the tunable wavelength range of the laser matrix material is determined by the gain bandwidth of the activated ions in the laser medium, the tunable range and efficiency of the laser are significantly limited. Obtaining a continuously tunable laser source from the infrared to the ultraviolet has become an unavoidable challenge in practical applications. Currently, a relatively effective method is to use visible and near-infrared all-solid-state lasers as the fundamental frequency source, utilizing the frequency doubling effect of nonlinear optical crystals to effectively extend and adjust the laser wavelength. Therefore, nonlinear optical crystals, as an important component of laser science, are widely used in information storage, modern science, and other fields. From the current development status of nonlinear optical crystal materials, the main focus of research into novel nonlinear optical crystals is continuously extending towards the ultraviolet and mid-to-far-infrared ends of the spectrum.

[0003] Developing all-solid-state deep ultraviolet (<200nm) coherent light sources is one of the most cutting-edge development directions in the international optoelectronic field. It plays a crucial role in advancing integrated photolithography and spectroscopy technologies, and also has significant application prospects and huge potential market demand in life sciences, medicine, military, and laser precision machining industries. In recent years, various crystals with the potential to directly output deep ultraviolet light have been discovered, such as RBBF, ABBF, and γ-BBF. However, since these crystals have not yet grown into large single crystals and have not undergone rigorous performance testing and laser frequency doubling experiments, KBBF crystals remain the most practically viable option. Given the huge demand for deep ultraviolet coherent light sources, it is crucial to develop and grow commercially viable deep ultraviolet crystals. Summary of the Invention

[0004] This invention provides a method for preparing magnesium malonate dihydrate and its nonlinear optical crystal, as well as its applications. The invention provides a novel compound, magnesium malonate dihydrate, and also provides that the magnesium malonate dihydrate crystal is a nonlinear optical crystal. The nonlinear optical crystal of this invention has good phase-matching ability; simultaneously, its ultraviolet absorption edge is 190 nm, thus the Mg(C3H2O4)·2H2O nonlinear optical crystal can achieve a second harmonic of Nd:YAG (λ=1.064μm).

[0005] This invention is achieved through the following technical solution:

[0006] Option 1)

[0007] A magnesium malonate dihydrate compound, wherein the chemical formula of the magnesium malonate dihydrate compound is Mg(C3H2O4)·2H2O.

[0008] Preferably, the magnesium malonate dihydrate compound is a nonlinear optical crystal, belonging to the orthorhombic crystal system, with space group Pca21 and cell parameters of [missing information]. α=γ=β=90°, Z=4;

[0009] Option 2)

[0010] The preparation method of magnesium malonate dihydrate includes the following steps: malonic acid and magnesium hydroxide are mixed in a molar ratio of 1:(1-1.5) and then added to water or ammonia water, and reacted at a reaction temperature of 80-180℃ for more than 1 day to obtain the magnesium malonate dihydrate compound. The total mass of the malonic acid and magnesium hydroxide and the volume ratio of ammonia water or water is (25-60) g:50 mL.

[0011] Furthermore, the molar ratio of malonic acid to magnesium hydroxide is 1:(1-1.5), preferably 1:(1-1.3); specifically 1:1.1, 1:1.2, and 1:1.3. Other ratios within the 1:(1-1.5) range can also be used to prepare the required single crystals according to the preparation method.

[0012] Furthermore, the total mass ratio of malonic acid and magnesium hydroxide to the volume ratio of ammonia is (25-60) g:50 mL, preferably (30-50) g:50 mL. Specifically, it can be 30 g:50 mL, 40 g:50 mL, or 50 g:50 mL.

[0013] Furthermore, the reaction temperature is 130-180℃; the reaction time is 7-30 days, preferably 140-160℃, specifically 145℃, but temperatures between 140-160℃ are acceptable. The preferred reaction time is 10-20 days.

[0014] Option 3)

[0015] The magnesium malonate dihydrate is used in the fabrication of lasers, ultraviolet harmonic generators, optical parametric and amplification devices, or optical waveguide devices. Preferably, the magnesium malonate dihydrate can be used to generate fourth harmonic light output from a laser beam with a wavelength of 1.064 μm. Preferably, the magnesium malonate dihydrate, such as magnesium malonate dihydrate crystal, can be used in optical parametric and amplification devices from the infrared to the ultraviolet regions.

[0016] Option 4)

[0017] An all-solid-state laser, the all-solid-state laser comprising the magnesium malonate dihydrate compound.

[0018] Compared with the prior art, the present invention has the following beneficial effects.

[0019] (1) This invention provides a magnesium malonate dihydrate compound with the chemical formula Mg(C3H2O4)·2H2O. The phase matching ability of Mg(C3H2O4)·2H2O was measured by using the powder frequency doubling test method. Its powder frequency doubling effect is 4.2 times that of KH2PO4 (KDP), which shows that the lithium dimethyl malonate hydrate nonlinear optical crystal prepared by this invention has a good phase matching ability. At the same time, its ultraviolet absorption edge is 190nm, so the Mg(C3H2O4)·2H2O nonlinear optical crystal can achieve the second harmonic of Nd:YAG (λ=1.064μm). Furthermore, it can be predicted that the Mg(C3H2O4)·2H2O crystal can be used for the third and fourth harmonic generators of Nd:YAG.

[0020] 2) The Mg(C3H2O4)·2H2O 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 short-wave ultraviolet band, so as to promote the development of related disciplines and industrial technologies. Attached Figure Description

[0021] Figure 1 The X-ray powder diffraction pattern of the Mg(C3H2O4)·2H2O single crystal obtained in Example 1 is shown.

[0022] Figure 2 This is a schematic diagram of the single-cell structure of Mg(C3H2O4)·2H2O crystal.

[0023] Figure 3 The image shows a crystal prepared in Example 2.

[0024] Figure 4 This is a typical schematic diagram of the nonlinear optical effect when Mg(C3H2O4)·2H2O crystal is used as a frequency doubling crystal. In the diagram, 1 is the laser, 2 is the incident laser beam, 3 is the processed single crystal, 4 is the outgoing laser beam, and 5 is the filter. Detailed Implementation

[0025] 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.

[0026] Unless otherwise stated, the raw materials and reagents used in the following examples are commercially available products or can be prepared by known methods.

[0027] In the following examples, the obtained Mg(C3H2O4)·2H2O single crystals were characterized using a Rigaku Mini-flex 600 powder diffractometer equipped with a Cu target; test conditions: room temperature.

[0028] Example 1

[0029] Mg(C3H2O4)·2H2O single crystal powder was prepared by isothermal evaporation reaction.

[0030] Raw materials used to prepare Mg(C3H2O4)·2H2O single crystal powder:

[0031] C3H4O4 2.082g (0.020mol)

[0032] MgCO3 1.855g (0.022mol)

[0033] The specific operating steps are as follows: After weighing the raw materials according to the above dosage in the operating box, mix them evenly, then add them to a 50mL beaker, add 25mL of deionized water, heat to 80℃, and filter out the excess MgCO3 raw material. Then put the beaker into an 80℃ oven and evaporate for 1 day to obtain Mg(C3H2O4)·2H2O single crystal powder.

[0034] The X-ray powder diffraction pattern of the Mg(C3H2O4)·2H2O single crystal prepared in this embodiment is as follows: Figure 1 As shown, the Mg(C3H2O4)·2H2O single crystal obtained in this embodiment is a single pure phase with high purity.

[0035] Its single-cell structure diagram is as follows Figure 2 As shown, the obtained Mg(C3H2O4)·2H2O single crystal does not have a center of symmetry, belongs to the orthorhombic crystal system, has a space group of Pca21, and a cell parameter of [missing information]. α=γ=β=90°, Z=4; unit cell volume is

[0036] Example 2

[0037] Mg(C3H2O4)·2H2O single crystals were prepared by hydrothermal reaction.

[0038] Raw materials used to prepare Mg(C3H2O4)·2H2O single crystals:

[0039] C3H4O4 15.615g (0.150mol)

[0040] 8.745g (0.150mol) of Mg(OH)₂

[0041] The specific operating steps are as follows: Weigh the raw materials according to the above dosage in the operating chamber, mix them evenly, add 50ml of ammonia water, then place it in a polytetrafluoroethylene liner, and finally put it into a stainless steel reactor (200ml). Immediately afterward, tighten the liner and place it in a 145℃ oven for 15 days to obtain 10×8×3mm Mg(C3H2O4)·2H2O single crystals. Figure 3 The image shown is a photograph of the crystal prepared in Example 2.

[0042] Example 3

[0043] Mg(C3H2O4)·2H2O single crystals were prepared by hydrothermal reaction.

[0044] Raw materials used to prepare Mg(C3H2O4)·2H2O single crystals:

[0045] C3H4O4 15.615g (0.150mol)

[0046] 8.745g (0.150mol) of Mg(OH)₂

[0047] The specific operating steps are as follows: After weighing the raw materials according to the above dosage in the operating box, mix them evenly, add 50ml of ammonia water, and then place them directly in a polytetrafluoroethylene liner. Then place them in a stainless steel reactor (200ml). Immediately afterward, tighten the container and place it in a 150℃ oven for 8 days to obtain 4×2×1mm Mg(C3H2O4)·2H2O single crystals.

[0048] The X-ray powder diffraction patterns of the compounds prepared in the above embodiments are all as follows: Figure 1 As shown, it was determined to be Mg(C3H2O4)·2H2O crystal.

[0049] Example 4

[0050] Mg(C3H2O4)·2H2O single crystals were prepared by hydrothermal reaction.

[0051] Raw materials used to prepare Mg(C3H2O4)·2H2O single crystals:

[0052] C3H4O4 15.615g (0.150mol)

[0053] 8.745g (0.150mol) of Mg(OH)₂

[0054] The specific operating steps are as follows: Weigh the raw materials according to the above dosage in the operating box, mix them evenly, add 50ml of ammonia water, then place it in a polytetrafluoroethylene liner, and then put it into a stainless steel reactor (200ml). Immediately afterward, tighten it and put it in a 130℃ oven for 15 days to obtain the magnesium malonate dihydrate.

[0055] Example 5

[0056] Mg(C3H2O4)·2H2O single crystals were prepared by hydrothermal reaction.

[0057] Raw materials used to prepare Mg(C3H2O4)·2H2O single crystals:

[0058] C3H4O4 15.615g (0.150mol)

[0059] Mg(OH)₂ 9.620g (0.165mol)

[0060] The specific operating steps are as follows: Weigh the raw materials according to the above dosage in the operating box, mix them evenly, add 50ml of ammonia water, then place it in a polytetrafluoroethylene liner, and then put it into a stainless steel reactor (200ml). Immediately afterward, tighten it and put it in a 130℃ oven for 15 days to obtain the magnesium malonate dihydrate.

[0061] Example 6

[0062] Mg(C3H2O4)·2H2O single crystals were prepared by hydrothermal reaction.

[0063] Raw materials used to prepare Mg(C3H2O4)·2H2O single crystals:

[0064] C3H4O4 15.615g (0.150mol)

[0065] Mg(OH)₂ 10.494g (0.180mol)

[0066] The specific operating steps are as follows: Weigh the raw materials according to the above dosage in the operating box, mix them evenly, add 50ml of ammonia water, then place it in a polytetrafluoroethylene liner, and then put it into a stainless steel reactor (200ml). Immediately afterward, tighten it and put it in a 130℃ oven for 15 days to obtain the magnesium malonate dihydrate.

[0067] Example 7

[0068] Mg(C3H2O4)·2H2O single crystals were prepared by hydrothermal reaction.

[0069] Raw materials used to prepare Mg(C3H2O4)·2H2O single crystals:

[0070] C3H4O4 32.013g (0.308mol)

[0071] Mg(OH)₂ 17.929g (0.308mol)

[0072] The specific operating steps are as follows: Weigh the raw materials according to the above dosage in the operating box, mix them evenly, add 50ml of ammonia water, then place it in a polytetrafluoroethylene liner, and then put it into a stainless steel reactor (200ml). Immediately afterward, tighten it and put it in a 130℃ oven for 15 days to obtain the magnesium malonate dihydrate.

[0073] Example 8

[0074] Mg(C3H2O4)·2H2O single crystals were prepared by hydrothermal reaction.

[0075] Raw materials used to prepare Mg(C3H2O4)·2H2O single crystals:

[0076] C3H4O4 38.462g (0.369mol)

[0077] Mg(OH)₂ 21.541g (0.369mol)

[0078] The specific operating steps are as follows: Weigh the raw materials according to the above dosage in the operating box, mix them evenly, add 50ml of ammonia water, then place it in a polytetrafluoroethylene liner, and then put it into a stainless steel reactor (200ml). Immediately afterward, tighten it and put it in a 130℃ oven for 15 days to obtain the magnesium malonate dihydrate.

[0079] Example 9

[0080] Mg(C3H2O4)·2H2O single crystals were prepared by hydrothermal reaction.

[0081] Raw materials used to prepare Mg(C3H2O4)·2H2O single crystals:

[0082] C3H4O4 15.615g (0.150mol)

[0083] Mg(OH)₂ 9.620g (0.165mol)

[0084] The specific operating steps are as follows: After weighing the raw materials according to the above dosage in the operating box, mix them evenly, add 50ml of ammonia water, then place it in a polytetrafluoroethylene liner, and then put it into a stainless steel reactor (200ml). Immediately afterwards, tighten it and put it in a 145℃ oven for 15 days to obtain the magnesium malonate dihydrate.

[0085] Example 10

[0086] Mg(C3H2O4)·2H2O single crystals were prepared by hydrothermal reaction.

[0087] Raw materials used to prepare Mg(C3H2O4)·2H2O single crystals:

[0088] C3H4O4 15.615g (0.150mol)

[0089] Mg(OH)₂ 10.494g (0.180mol)

[0090] The specific operating steps are as follows: After weighing the raw materials according to the above dosage in the operating box, mix them evenly, add 50ml of ammonia water, then place it in a polytetrafluoroethylene liner, and then put it into a stainless steel reactor (200ml). Immediately afterwards, tighten it and put it in a 140℃ oven for 15 days to obtain the magnesium malonate dihydrate.

[0091] Example 11

[0092] Mg(C3H2O4)·2H2O single crystals were prepared by hydrothermal reaction.

[0093] Raw materials used to prepare Mg(C3H2O4)·2H2O single crystals:

[0094] C3H4O4 7.808g (0.075mol)

[0095] Mg(OH)₂ 4.373g (0.075mol)

[0096] The specific operating steps are as follows: After weighing the raw materials according to the above dosage in the operating box, mix them evenly, add 50ml of ammonia water, then place it in a polytetrafluoroethylene liner, and then put it into a stainless steel reactor (200ml). Immediately afterwards, tighten it and put it in a 160℃ oven for 15 days to obtain the magnesium malonate dihydrate.

[0097] Example 12

[0098] Mg(C3H2O4)·2H2O single crystals were prepared by hydrothermal reaction.

[0099] Raw materials used to prepare Mg(C3H2O4)·2H2O single crystals:

[0100] C3H4O4 7.808g (0.075mol)

[0101] Mg(OH)₂ 6.560g (0.113mol)

[0102] The specific operating steps are as follows: After weighing the raw materials according to the above dosage in the operating box, mix them evenly, add 90ml of ammonia water, then place it in a polytetrafluoroethylene liner, and then put it into a stainless steel reactor (200ml). Immediately afterwards, tighten it and put it in a 180℃ oven for 15 days to obtain the magnesium malonate dihydrate.

[0103] The Mg(C3H2O4)·2H2O crystals prepared in the above examples all have the following properties: Figure 2 The cell structure shown.

[0104] The powder frequency doubling effect of the Mg(C3H2O4)·2H2O crystals prepared in the above examples is 4.2 times that of KH2PO4(KDP).

[0105] The ultraviolet absorption edge of the Mg(C3H2O4)·2H2O crystal prepared in the above examples is 190 nm; that is, the Mg(C3H2O4)·2H2O crystal is a short-wave ultraviolet frequency doubling optical crystal.

[0106] All of the above examples can prepare colorless and transparent Mg(C3H2O4)·2H2O crystals. Figure 3 The image shown is a photograph of the crystal prepared in Example 2.

[0107] Frequency multiplication test experiment as follows Figure 4 As shown, the [Li2C5O4H6]2·3H2O crystal obtained in Example 2 was processed, cut, oriented, polished, and then placed in... Figure 4 At position 3 in the device shown, at room temperature, a Q-switched Nd:YAG laser is used as laser 1 (i.e., input light source). The incident wavelength of the incident laser beam 2 is 1064nm. After the incident laser beam 2 passes through the single crystal 3, which undergoes crystal post-processing and optical processing, it is observed that the outgoing laser beam 4, after passing through the filter 5, exhibits a significant 532nm frequency-doubled green light output. The output intensity (powder frequency doubling effect) of the Mg(C3H2O4)·2H2O crystal in Example 2 of the specification is approximately 4.2 times that of KDP under the same conditions.

[0108] Using the frequency-doubled light of a Q-switched Nd:YAG laser as the input light source, with an incident wavelength of 532nm, a significant 266nm frequency-doubled ultraviolet light output was observed.

[0109] 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. A method for preparing a magnesium malonate dihydrate nonlinear optical crystal, characterized in that: The aforementioned magnesium malonate dihydrate nonlinear optical crystal has the chemical formula Mg(C3H2O4)·2H2O; it belongs to the orthorhombic crystal system and has the space group [missing information]. Pca2 1 The unit cell parameters are a = 9.3968 (2) Å, b = 7.2457 (1) Å, c = 8.1444(2) Å, α = γ = β =90°, Z = 4; V = 554.52(2) Å 3 ; The preparation method includes the following steps: malonic acid and magnesium hydroxide are mixed in a molar ratio of 1:(1-1.5) and then added to ammonia water, and reacted at a reaction temperature of 130-180℃ for more than 1 day to obtain the magnesium malonate dihydrate compound. The total mass of the malonic acid and magnesium hydroxide and the volume ratio of ammonia water or water is (8~60) g:50 mL.

2. The method for preparing a magnesium malonate dihydrate nonlinear optical crystal according to claim 1, wherein the molar ratio of malonic acid to magnesium hydroxide is 1:(1-1.3).

3. The method for preparing a magnesium malonate dihydrate nonlinear optical crystal according to claim 1, characterized in that: The total mass of malonic acid and magnesium hydroxide to the volume ratio of ammonia water is (25~50) g: 50 mL.

4. The method for preparing a magnesium malonate dihydrate nonlinear optical crystal according to claim 1, characterized in that: The reaction temperature is 140-160℃.

5. The use of a magnesium malonate dihydrate nonlinear optical crystal prepared by the preparation method according to any one of claims 1-4, characterized in that: The magnesium malonate dihydrate nonlinear optical crystal is used to fabricate lasers.

6. The use of a magnesium malonate dihydrate nonlinear optical crystal prepared by the preparation method according to any one of claims 1-4, characterized in that: The aforementioned magnesium malonate dihydrate nonlinear optical crystal is used to fabricate ultraviolet harmonic generators, optical parametric and amplification devices, or optical waveguide devices.

7. An all-solid-state laser, characterized in that: The all-solid-state laser comprises a magnesium malonate dihydrate nonlinear optical crystal prepared by the preparation method according to any one of claims 1-4.

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