A potassium aminodiacetate compound, and a nonlinear optical crystal, a preparation method and a use thereof

Abstract

This invention relates to a potassium aminodiacetate compound and its nonlinear optical crystal, preparation method, and uses. The crystal has the molecular formula K[NH2(CH2COO)2], and the K[NH2(CH2COO)2] crystal does not have a center of symmetry, belongs to the monoclinic crystal system, has a space group of P21, and has cell parameters α = γ = 90°, β = 98.686°. The nonlinear optical crystal of this invention has good phase matching ability; at the same time, its ultraviolet absorption edge is 208 nm, therefore the K[NH2(CH2COO)2] nonlinear optical crystal can achieve the second harmonic of Nd:YAG (λ = 1.064 μm); and it can be predicted that the K[NH2(CH2COO)2] crystal can be used for the third and fourth harmonic generators of Nd:YAG.

Description

Technical Field

[0001] This invention relates to a potassium aminodiacetate compound and its nonlinear optical crystal, preparation method and uses, and is applied in the field of novel optoelectronic functional materials. Background Technology

[0002] Optical materials have a wide range of applications in the field of novel functional materials. Among them, ultraviolet lasers are not only used in laser precision processing, semiconductors, and optical information storage, but also play a significant role in medical laser therapy. Currently, based on their working medium, these materials can be divided into three main categories: gas lasers, semiconductor lasers, and all-solid-state lasers.

[0003] Among these lasers, commonly used gas lasers include He-Gd lasers in the ultraviolet (UV) band, He-Ne lasers in the visible (VIS) band, and CO2 lasers in the infrared (IR) band. Semiconductor lasers also have corresponding materials from ultraviolet to far-infrared, mainly depending on the size of the band gap in the active region of the semiconductor material. Semiconductor materials in the ultraviolet (UV) band include AlN and AlGaN; those in the visible (VIS) band include AlInGaN and GaInP; and those in the infrared (IR) band include GaInP / AlGaInP, InGaAsP, and InGaAsP. All-solid-state lasers are mainly classified according to the laser material into ultraviolet (LBO, BBO), visible (VIS) band (Ti:Sapphire lasers), near-infrared (NIR) band (Yb:YAG), and mid-infrared (MIR) band (Er:YAG, Er:YAG).

[0004] Gas lasers typically have a large size due to the need for gas storage and circulation systems, and the regular gas replacement and maintenance significantly increase operating costs. Semiconductor lasers have always suffered from severe heat dissipation problems during applications, making it difficult to achieve the expected output power. In contrast, all-solid-state lasers generally have significant advantages in terms of power, efficiency, size, and wavelength flexibility.

[0005] In their early applications, all-solid-state lasers were often limited by their low output power, hindering their widespread adoption. However, in the last decade or so, with advancements in ultraviolet laser crystals and nonlinear frequency conversion, a number of high-power, high-efficiency ultraviolet solid-state lasers have been developed. Currently, the average output power of a 355nm all-solid-state ultraviolet laser has been tuned to 17.7W, and laser processing equipment based on this technology has entered the industrialization stage and is already in use.

[0006] However, the direct absorption of light from longer wavelengths of ultraviolet light into materials and the diffusion of thermal effects cannot yet meet the growing demand, posing a significant challenge to the cold processing field. To address this need, many well-known laser companies worldwide are focusing on the industrialization of all-solid-state lasers in the short-wavelength ultraviolet range below 250nm. For all-solid-state lasers in the short-wavelength ultraviolet range, the key to achieving short-wavelength ultraviolet nonlinear optical (NLO) lasers lies in developing and growing novel short-wavelength ultraviolet nonlinear optical (NLO) crystals that meet this requirement.

[0007] To achieve higher manufacturing precision, shorter wavelengths and higher quality light beams are essential. Therefore, developing and preparing short-wavelength NLO materials with excellent properties is a crucial step in advancing this field. Summary of the Invention

[0008] This invention provides a potassium aminodiacetate compound and its nonlinear optical crystal, preparation method and uses. The invention prepares a compound and crystal with the chemical formula K[NH2(CH2COO)2]. The potassium aminodiacetate nonlinear optical crystal of this invention has good phase matching ability and an ultraviolet absorption edge of 201 nm, so this crystal is expected to be used in Nd lasers.

[0009] This invention is achieved through the following technical solution:

[0010] Option 1)

[0011] A potassium aminodiacetate compound with the chemical formula K[NH2(CH2COO)2].

[0012] Option 2)

[0013] The preparation method of potassium aminodiacetate includes the following steps: dissolving iminodiacetic acid and potassium hydroxide in a molar ratio of (1-1.5):1 in a solvent, and then reacting at 25-120℃ for 7-30 days to obtain potassium aminodiacetate.

[0014] Preferably, the solvent is deionized water. The molar ratio of iminodiacetic acid and potassium hydroxide can be 1:1, 1.2:1, 1.4:1, or 1.5:1.

[0015] The total mass ratio of iminodiacetic acid and potassium hydroxide to the volume ratio of the solvent is (30-90) g: 100 mL.

[0016] Option 3)

[0017] A potassium aminodiacetate nonlinear optical crystal, the crystal having the molecular formula K[NH2(CH2COO)2], lacking a center of symmetry, belonging to the monoclinic crystal system, with space group P21 and cell parameters of [missing information]. α=γ=90°, β=98.686°, z=2.

[0018] Option 4)

[0019] A method for preparing potassium aminodiacetate nonlinear optical crystals includes the following steps: dissolving iminodiacetic acid and potassium hydroxide in a molar ratio of 1-1.5:1 in a solvent, and then reacting at 25-120℃ for 7-30 days to obtain potassium aminodiacetate compound; then dissolving the potassium aminodiacetate compound in a solvent, and then evaporating it at a constant temperature of 30-60℃ for 7-30 days to obtain the potassium aminodiacetate nonlinear optical crystal.

[0020] Option 5)

[0021] The method for preparing the potassium aminodiacetate nonlinear optical crystal includes the following steps: dissolving iminodiacetic acid and potassium hydroxide in a molar ratio of (1-1.5):1 in a solvent, and then reacting at 25-120℃ for 7-30 days to obtain the potassium aminodiacetate compound; then dissolving the potassium aminodiacetate compound in a solvent, and then reacting at a constant temperature of 30-60℃ for 7-30 days to obtain the potassium aminodiacetate nonlinear optical crystal.

[0022] Option 6)

[0023] The application of a potassium aminodiacetate nonlinear optical crystal, wherein the potassium aminodiacetate nonlinear optical crystal is used to prepare optical devices, the optical devices including all-solid-state lasers, harmonic generators, optical parametric and amplification devices or optical waveguide devices.

[0024] An optical device comprising the aforementioned potassium aminodiacetate nonlinear optical crystal.

[0025] Compared with the prior art, the present invention has the following beneficial effects.

[0026] (1) This invention provides a potassium aminodiacetate compound with the chemical formula K[NH2(CH2COO)2]. The phase matching ability of K[NH2(CH2COO)2] was measured by using the powder frequency doubling test method. As shown in the figure, its powder frequency doubling effect is 3 times that of KH2PO4(KDP), which indicates that the potassium aminodiacetate nonlinear optical crystal prepared by this invention has good phase matching ability. At the same time, its ultraviolet absorption edge is 201nm, and the K[NH2(CH2COO)2] nonlinear optical crystal can achieve a second harmonic of Nd:YAG (λ=1.064μm).

[0027] (2) The K[NH2(CH2COO)2] single crystal prepared by this invention is colorless and transparent and does not deliquesce. 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

[0028] Figure 1 The X-ray powder diffraction pattern of the K[NH2(CH2COO)2] single crystal obtained in Example 1 is shown.

[0029] Figure 2 This is a schematic diagram of the unit cell structure of K[NH2(CH2COO)2] crystal.

[0030] Figure 3 This is a typical schematic diagram of the nonlinear optical effects of K[NH2(CH2COO)2] crystal when used as a frequency doubling crystal.

[0031] 1 is the laser, 2 is the incident laser beam, 3 is the processed single crystal, 4 is the emitted laser beam, and 5 is the filter.

[0032] Figure 4 The frequency doubling effect diagram for K[NH2(CH2COO)2] crystals with different particle sizes.

[0033] Figure 5 Ultraviolet transmission spectrum of K[NH2(CH2COO)2] crystal

[0034] Figure 6 Photograph of K[NH2(CH2COO)2] crystal obtained in Example 6 Detailed Implementation

[0035] 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.

[0036] Unless otherwise stated, the raw materials and reagents used in the following examples are commercially available products or can be prepared by known methods.

[0037] Example 1

[0038] The preparation method of the potassium aminodiacetate compound in this embodiment includes the following steps: dissolving iminodiacetic acid and potassium hydroxide in a molar ratio of 1:1 in a solvent, and then reacting at 25°C for 30 days to obtain the potassium aminodiacetate compound. The solvent is deionized water; the total mass ratio of iminodiacetic acid and potassium hydroxide to the volume ratio of the solvent is 30 g: 100 mL. This embodiment yields the potassium aminodiacetate compound.

[0039] Example 2

[0040] A method for preparing potassium aminodiacetate includes the following steps: dissolving iminodiacetic acid and potassium hydroxide in a molar ratio of 1.2:1 in a solvent, and then reacting at 50°C for 20 days to obtain the potassium aminodiacetate compound. The solvent is deionized water; the total mass ratio of iminodiacetic acid and potassium hydroxide to the volume ratio of the solvent is 40 g: 100 mL. This example yielded the potassium aminodiacetate compound.

[0041] Example 3

[0042] A method for preparing potassium aminodiacetate includes the following steps: dissolving iminodiacetic acid and potassium hydroxide in a molar ratio of 1.4:1 in a solvent, and then reacting at 100°C for 10 days to obtain the potassium aminodiacetate compound. The solvent is deionized water; the total mass ratio of iminodiacetic acid and potassium hydroxide to the volume ratio of the solvent is 80 g: 100 mL. This example yielded the potassium aminodiacetate compound.

[0043] Example 4

[0044] A method for preparing potassium aminodiacetate includes the following steps: dissolving iminodiacetic acid and potassium hydroxide in a molar ratio of 1.5:1 in a solvent, and then reacting at 120°C for 7 days to obtain the potassium aminodiacetate compound. The solvent is deionized water; the total mass ratio of iminodiacetic acid and potassium hydroxide to the volume ratio of the solvent is 90 g: 100 mL. This example yielded the potassium aminodiacetate compound.

[0045] Example 5

[0046] The potassium aminodiacetate compound obtained in Example 1 was dissolved in a solvent and then evaporated at a constant temperature of 30°C for 30 days to obtain the potassium aminodiacetate nonlinear optical crystal. A K[NH2(CH2COO)2] single crystal with a size of 5×5×1mm was obtained.

[0047] The obtained K[NH2(CH2COO)2] single crystal was characterized using a Rigaku Mini-flex 600 powder diffractometer equipped with a Cu target; test conditions: room temperature. The X-ray powder diffraction pattern of the K[NH2(CH2COO)2] single crystal prepared in this embodiment is shown below. Figure 1As shown, the K[NH2(CH2COO)2] single crystal obtained in this embodiment is a single pure phase with high purity.

[0048] Its single-cell structure diagram is as follows Figure 2 As shown, the obtained K[NH2(CH2COO)2] crystal does not have a center of symmetry, belongs to the monoclinic crystal system, has a space group of P21, and a unit cell parameter of... α=γ=90°, β=98.686°, Z=2,

[0049] Example 6

[0050] The potassium aminodiacetate compound obtained in Example 4 was dissolved in a solvent and then evaporated at 60°C for 7 days to obtain the potassium aminodiacetate nonlinear optical crystal. A K[NH2(CH2COO)2] single crystal with dimensions of 15×10×5mm was obtained. The X-ray powder diffraction pattern of the K[NH2(CH2COO)2] single crystal obtained in this example is also consistent with... Figure 1 Consistent.

[0051] Example 7

[0052] The potassium aminodiacetate compound obtained in Example 2 was dissolved in a solvent and then evaporated at a constant temperature of 40°C for 7-30 days to obtain the potassium aminodiacetate nonlinear optical crystal. The X-ray powder diffraction pattern of the K[NH2(CH2COO)2] single crystal prepared in this example is also consistent with... Figure 1 Consistent.

[0053] Example 8

[0054] The potassium aminodiacetate compound obtained in Example 3 was dissolved in a solvent and then evaporated at a constant temperature of 50°C for 7-30 days to obtain the potassium aminodiacetate nonlinear optical crystal. The X-ray powder diffraction pattern of the K[NH2(CH2COO)2] single crystal prepared in this example is also consistent with... Figure 1 Consistent.

[0055] Figure 6 Photograph of K[NH2(CH2COO)2] crystal obtained in Example 6

[0056] The K[NH2(CH2COO)2] crystal sample obtained in Example 6 was subjected to a frequency doubling test experiment, and the results are as follows: Figure 4 As shown. Frequency doubling tests were also performed on crystal samples from other embodiments, and... Figure 4 Basically the same.

[0057] The K[NH2(CH2COO)2] crystal obtained in Example 6 was processed, cut, oriented, polished, and then placed in... Figure 3At 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 has undergone crystal post-processing and optical processing, it is observed that the outgoing laser beam 4, after passing through the filter 5, is a significant 532nm frequency-doubled green light output. The output intensity (powder frequency doubling effect) of the K[NH2(CH2COO)2] crystal in Example 6 of the specification is about 3 times that of KDP under the same conditions.

[0058] Figure 5 The ultraviolet transmission spectrum of the K[NH2(CH2COO)2] crystal is shown in the figure. As can be seen, the ultraviolet absorption edge is 201 nm. Using a frequency-doubled light source from a Q-switched Nd:YAG laser as the input light source, with an incident wavelength of 532 nm, a significant 266 nm frequency-doubled ultraviolet light output was observed. This indicates that the K[NH2(CH2COO)2] nonlinear optical crystal can achieve second harmonic generation of Nd:YAG (λ=1.064μm). Furthermore, it can be predicted that the K[NH2(CH2COO)2] crystal can be used in third and fourth harmonic generators of Nd:YAG.

[0059] 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 potassium aminodiacetate nonlinear optical crystal, characterized by: The crystal has the molecular formula K[NH2(CH2COO)2], lacks a center of symmetry, belongs to the monoclinic crystal system, and has the space group K[NH2(CH2COO)2]. P2 1 The unit cell parameters are a = 5.6624(1) Å, b = 7.1938(1) Å, c = 8.6177(1)Å, α = γ = 90°, β =98.686°, z=2.

2. The method for preparing the potassium aminodiacetate nonlinear optical crystal according to claim 1, characterized in that: The process includes the following steps: dissolving iminodiacetic acid and potassium hydroxide in a molar ratio of 1-1.5:1 in a solvent, and then reacting them at 25-120°C for 7-30 days to obtain a potassium aminodiacetic acid compound; then dissolving the potassium aminodiacetic acid compound in a solvent, and then evaporating it at a constant temperature of 30-60°C for 7-30 days to obtain the potassium aminodiacetic acid nonlinear optical crystal.

3. Use of a potassium aminodiacetate nonlinear optical crystal, characterized in that: The potassium aminodiacetate nonlinear optical crystal of claim 1 is used to prepare optical devices, the optical devices including all-solid-state lasers, harmonic generators, optical parametric amplifiers or optical waveguides.

4. An optical device, characterized by: Including the potassium aminodiacetate nonlinear optical crystal as described in claim 1.

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