C (NH2) 3H2PO3 compound as well as crystal, preparation method and application thereof

Abstract

The invention discloses a C (NH2) 3H2PO3 compound, a crystal thereof, a preparation method and application of the C (NH2) 3H2PO3 compound in nonlinear optics, the C (NH2) 3H2PO3 compound and the crystal thereof provided by the invention are characterized in that the crystal structure is formed by mutually connecting [C (NH2) 3] < + > of a plane triangle and [H2PO3] <-> of a polar tetrahedron through hydrogen bonds; the synergistic effect of the two contributes to the nonlinear optical effect of the crystal.

Description

Technical Field

[0001] The present invention belongs to the technical field of functional crystal materials and particularly relates to a C(NH 2 ) 3 H 2 PO 3 Compounds and their crystals, preparation methods and applications in nonlinear optics. Background Art

[0002] Nonlinear optical crystal materials can efficiently generate coherent light with photon energy. Ultraviolet nonlinear optical crystals can convert long-wavelength lasers into short-wavelength ultraviolet lasers with higher photon energy through direct frequency doubling technology, playing an important role in cutting-edge scientific research equipment, precision processing, secure communications, laser medical treatment and many other fields. The development of ultraviolet nonlinear optical crystals provides strong support for the development of laser technology.

[0003] Currently, nonlinear optical crystals that can be used for 266nm short-wavelength ultraviolet laser output are still in short supply. Exploring new ultraviolet nonlinear optical crystals with excellent comprehensive properties such as wide bandgap, large frequency doubling effect and moderate birefringence is an important and challenging task in the field of optoelectronic functional crystals. Summary of the invention

[0004] In order to solve the above technical problems, the present invention provides a chemical formula of C(NH 2 ) 3 H 2 PO 3 of compounds.

[0005] The present invention also provides the above chemical formula C(NH 2 ) 3 H 2 PO 3 A method for preparing a compound comprising: 2 ) 3 The compound and the P-containing compound are mixed and reacted in a solvent to prepare the compound.

[0006] According to an embodiment of the present invention, the C(NH 2 ) 3 The compound is selected from [C(NH 2 ) 3 ] 2 CO 3 , C(NH 2 ) 3 HCO 3 , C(NH 2 ) 3 Cl, C(NH 2 ) 3 NO3 or C(NH 2 ) 3 H 2 PO 4 At least one of 2 ) 3 ] 2 CO 3 .

[0007] According to an embodiment of the present invention, the P-containing compound is selected from H 3 PO 3 , KH 2 PO 3 and H 3 PO 2 At least one of, preferably H 3 PO 3 .

[0008] According to an embodiment of the present invention, the C(NH 2 ) 3 Compounds, compounds containing P, n(C(NH 2 ) 3 ):n(P)=(1~3):(1~3); exemplary are 1:1, 1.2:1, 1.4:1, 1:1.2, 1:1.4.

[0009] According to an embodiment of the present invention, the solvent may be selected from an organic solvent or an inorganic solvent, preferably an inorganic solvent, such as water, exemplified by deionized water.

[0010] According to an embodiment of the present invention, the C(NH 2 ) 3 The mass volume ratio of the sum of the mass of the compound and the P-containing compound to the solvent can be (10-90) g:100 mL, preferably (20-70) g:100 mL; exemplary are 17 g:100 mL, 34 g:100 mL, 51 g:100 mL, and 68 g:100 mL.

[0011] According to an embodiment of the present invention, the reaction temperature may be 20-95°C, preferably 20-60°C, for example 20°C, 30°C, 40°C, 50°C, 55°C, 60°C; the reaction time may be 5-30 days, preferably 8-20 days.

[0012] Furthermore, the method also includes cooling the reaction liquid after the mixed reaction. For example, the cooling rate can be 0.5 to 20°C / h, exemplified by 0.5°C / h, 1°C / h, 2°C / h, 3°C / h, 4°C / h, 6°C / h, 8°C / h or 10°C / h.

[0013] The present invention also provides a nonlinear optical crystal, the chemical formula of which is C(NH 2 ) 3 H 2 PO 3 , that is, the nonlinear optical crystal is C(NH 2 ) 3 H 2 PO 3 Crystal.

[0014] According to an embodiment of the present invention, the nonlinear optical crystal belongs to the monoclinic system and has the following characteristics: Figure 1 The crystal structure shown has a space group of P2 1 , the unit cell parameters are α=γ=90°, β=100.639(16)°, Z=2.

[0015] According to an embodiment of the present invention, the nonlinear optical crystal is composed of [C(NH 2 ) 3 ] + and [H 2 PO 3 ] - are connected to each other by hydrogen bonds. For example, the nonlinear optical crystal is composed of planar triangular [C(NH 2 ) 3 ] + and polar tetrahedral [H 2 PO 3 ] - They are connected to each other by hydrogen bonds.

[0016] According to an embodiment of the present invention, the nonlinear optical crystal has the following Figure 2 X-ray diffraction pattern shown.

[0017] According to an embodiment of the present invention, the powder frequency doubling effect of the nonlinear optical nonlinear optical crystal is KH 2 PO 4 (KDP) is 1.6 times.

[0018] According to the embodiment of the present invention, the ultraviolet absorption cut-off wavelength of the nonlinear optical crystal can reach 200 nm, that is, the nonlinear optical crystal has the potential to be used in the wavelength band above 200 nm.

[0019] According to the embodiment of the present invention, the nonlinear optical crystal can achieve a higher transmittance, and the band gap of the crystal is 6.20 eV.

[0020] The present invention also provides a method for preparing the nonlinear optical crystal, the method comprising:

[0021] The C(NH 2 ) 3 The compound and the P-containing compound are mixed and reacted in a solvent, and heated and evaporated to obtain the crystal.

[0022] Preferably, the C(NH 2 ) 3 The compound and the P-containing compound are mixed and reacted in a solvent. After the reaction is completed, the obtained product is dissolved in the solvent again, heated and evaporated to obtain the crystal.

[0023] Preferably, the C(NH 2 ) 3 The selection of the compound, the P-containing compound and the solvent is respectively the same as the above chemical formula C(NH 2 ) 3 H 2 PO 3 The method for preparing the compound is consistent with the selection.

[0024] According to an embodiment of the present invention, the reaction temperature is 20-95° C., and the reaction time is 5-30 days.

[0025] According to an embodiment of the present invention, the preparation method further comprises: cooling the reaction solution after heating and evaporation; and further comprises the steps of separation, filtration and drying to obtain the crystals.

[0026] For example, the cooling rate is 0.5 to 10°C / h, exemplified by 0.5°C / h, 1°C / h, 3°C / h, 5°C / h, 6°C / h, 8°C / h or 10°C / h.

[0027] According to an embodiment of the present invention, the method for preparing the nonlinear optical crystal specifically comprises the following steps:

[0028] Guanidine carbonate and phosphorous acid in a molar ratio of (1-1.5):1 are dissolved in a solvent, and then reacted at 20-95°C for 5-30 days to obtain C(NH 2 ) 3 H 2 PO 3 Compound; then the C(NH 2 ) 3 H 2 PO 3 The compound is dissolved in a solvent and then reacted at a constant temperature of 30 to 95° C. for 7 to 30 days to obtain the C(NH 2 ) 3 H 2 PO 3 Nonlinear optical crystals.

[0029] The present invention also provides applications of the crystal in the fields of laser frequency doubling, electro-optic modulation, photorefractive information processing and information storage; preferably, the crystal is used in a frequency doubling device in an all-solid-state laser.

[0030] According to the embodiment of the present invention, the nonlinear optical crystal can be used as an optical device in the ultraviolet-near infrared optical band.

[0031] Beneficial effects of the present invention:

[0032] In the borate system, the π-conjugated BO 3 The planar triangular group has a wide band gap and a large microscopic second-order polarizability, and is considered to be one of the most excellent nonlinear optical active groups in borates. Its coplanar arrangement is conducive to the synthesis of nonlinear optical crystals with large band gaps and frequency doubling coefficients. 2 BO 3 F 2 (KBBF) and BaB 2 O 4 (BBO) and other crystals contain this group. [C(NH 2 ) 3 ] + The group has BO 3 The π-conjugated planar triangular configuration with similar groups has outstanding nonlinear optical properties. The phosphite group is a polar tetrahedron formed by replacing one of the O atoms with an H atom on the basis of phosphate, which is conducive to the increase of nonlinear coefficient and birefringence. The present invention uses a combination of two groups to form a novel metal-free short-wave ultraviolet nonlinear optical crystal guanidine phosphite C (NH 2 ) 3 H 2 PO 3 .

[0033] (1) The present invention provides a novel guanidine phosphite C(NH 2 ) 3 H 2 PO 3 Compound and crystal thereof, the crystal structure of which consists of a planar triangular [C(NH 2 ) 3 ] + and polar tetrahedral [H 2 PO 3 ] - They are connected to each other by hydrogen bonds; the synergistic effect of the two contributes to the nonlinear optical effect of the crystal.

[0034] (2) C(NH 2 ) 3 H 2 PO 3The crystal outputs strong 532nm light under 1064nm laser irradiation, and its powder frequency doubling effect is KH 2 PO 4 (KDP) is 1.6 times that of the original device and phase matching can be achieved.

[0035] (3) C(NH 2 ) 3 H 2 PO 3 The crystal has a wide light transmittance range, and the ultraviolet cutoff edge can reach 200nm. It can be applied to the band above 200nm and has potential application prospects in nonlinear optics, laser technology, electro-optic modulation, photorefractive information processing and information storage.

[0036] (4) C(NH 2 ) 3 H 2 PO 3 The physical and chemical properties of the crystal are stable.

[0037] (5) C(NH 2 ) 3 H 2 PO 3 The preparation method of the compound and the crystal is simple in process, and is easy to grow large-sized single crystals. The crystals do not absorb moisture, grow quickly, and have low costs. BRIEF DESCRIPTION OF THE DRAWINGS

[0038] Figure 1 The present invention C(NH 2 ) 3 H 2 PO 3 Schematic diagram of the crystal structure of a crystal.

[0039] Figure 2 This is a comparison chart of the X-ray diffraction simulation spectrum obtained by fitting the crystal structure of the sample in Example 2 according to the single crystal X-ray diffraction data and the powder X-ray diffraction of the sample in Example 2.

[0040] Figure 3 Schematic diagram of frequency doubling test, where 1 is a laser, 2 is an incident laser beam, and 3 is C(NH 2 ) 3 H 2 PO 3 The crystal, 4 is the outgoing laser beam generated, and 5 is a photomultiplier tube equipped with a filter.

[0041] Figure 4 This is the frequency doubling test result of the sample in Example 2.

[0042] Figure 5 This is the UV-visible-near infrared diffuse reflectance diagram of the sample in Example 2.

[0043] Figure 6 This is the infrared spectrum of the sample in Example 2.

[0044] Figure 7 This is a crystal photograph of the sample in Example 5. DETAILED DESCRIPTION

[0045] The technical scheme of the present invention will be further described in detail below in conjunction with specific embodiments. It should be understood that the following embodiments are only exemplary descriptions and explanations 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 included in the scope that the present invention is intended to protect.

[0046] Unless otherwise specified, the raw materials and reagents used in the following examples are commercially available or can be prepared by known methods.

[0047] Example 1C (NH 2 ) 3 H 2 PO 3 Preparation of compounds

[0048] In this embodiment, C(NH 2 ) 3 H 2 PO 3 The preparation method of the compound comprises the following steps: mixing guanidine carbonate ([C(NH 2 ) 3 ] 2 CO 3 ) and phosphorous acid are dissolved in a solvent and then reacted at 25 °C for 10 days to obtain C(NH 2 ) 3 H 2 PO 3 The solvent is deionized water; the volume ratio of the total mass of the guanidine carbonate and the phosphorous acid to the solvent is 20g:100ml.

[0049] Example 2C (NH 2 ) 3 H 2 PO 3 Crystal preparation

[0050] In this embodiment, C(NH 2 ) 3 H 2 PO 3 The preparation method of the crystal comprises the following steps: dissolving guanidine carbonate and phosphorous acid in a molar ratio of 1.2:1 in a solvent, and then reacting at 30°C for 10 days to obtain C(NH 2 ) 3H 2 PO 3 The solvent is deionized water; the volume ratio of the total mass of the guanidine carbonate and the phosphorous acid to the solvent is 25g:100ml.

[0051] Example 3C (NH 2 ) 3 H 2 PO 3 Crystal preparation

[0052] In this embodiment, C(NH 2 ) 3 H 2 PO 3 The preparation method of the crystal comprises the following steps: dissolving guanidine carbonate and phosphorous acid in a molar ratio of 1.4:1 in a solvent, and then reacting at 50°C for 10 days to obtain C(NH 2 ) 3 H 2 PO 3 The solvent is deionized water; the volume ratio of the total mass of the guanidine carbonate and the phosphorous acid to the solvent is 30g:100ml.

[0053] Example 4C (NH 2 ) 3 H 2 PO 3 Crystal preparation

[0054] In this embodiment, C(NH 2 ) 3 H 2 PO 3 The preparation method of the crystal comprises the following steps: dissolving guanidine carbonate and phosphorous acid in a molar ratio of 1:1.2 in a solvent, and then reacting at 30°C for 10 days to obtain C(NH 2 ) 3 H 2 PO 3 The solvent is deionized water; the volume ratio of the total mass of the guanidine carbonate and the phosphorous acid to the solvent is 25g:100ml.

[0055] Example 5C (NH 2 ) 3 H 2 PO 3 Crystal preparation

[0056] In this embodiment, C(NH 2 ) 3 H 2 PO 3The preparation method of the crystal comprises the following steps: dissolving guanidine carbonate and phosphorous acid in a molar ratio of 1:1.4 in a solvent, and then reacting at 50°C for 10 days to obtain C(NH 2 ) 3 H 2 PO 3 The solvent is deionized water; the volume ratio of the total mass of the guanidine carbonate and the phosphorous acid to the solvent is 30g:100ml.

[0057] Example 6C (NH 2 ) 3 H 2 PO 3 Crystal preparation

[0058] The guanidine phosphite compound (i.e., C(NH 2 ) 3 H 2 PO 3 Compound) was dissolved in solvent water and then evaporated at 30°C for 30 days to obtain the C(NH 2 ) 3 H 2 PO 3 Nonlinear optical crystal. The size of C(NH 2 ) 3 H 2 PO 3 Single crystal.

[0059] The C(NH 2 ) 3 H 2 PO 3 The schematic diagram of the crystal structure is as follows Figure 1 As shown, the crystal belongs to the monoclinic system and the space group is P2 1 , the unit cell parameters are α=γ=90°, β=100.639(16)°, Z=2.

[0060] The C(NH 2 ) 3 H 2 PO 3 The crystal consists of triangular planar [C(NH 2 ) 3 ] + and [H 2 PO 3 ] - They are connected to each other by hydrogen bonds.

[0061] Example 7C (NH 2 ) 3 H 2PO 3 Crystal structure analysis and phase analysis

[0062] The C(NH 2 ) 3 H 2 PO 3 The crystal samples were subjected to structural analysis. Single crystal X-ray diffraction was performed on a Synergy Custom (Liquid Metal Jet D2+) X-ray single crystal diffractometer from Rigaku Corporation, Japan. The data collection temperature was 293K, and the diffraction light source was Ga-Kα radiation from a liquid metal target. The scanning mode was ω=2θ, and the data were processed for absorption correction using the Multi-Scan method. The structural analysis was completed using the SHELXTL program package; the positions of heavy atoms were determined using the direct method, and the coordinates of the remaining atoms were obtained using the difference Fourier synthesis method; the F-based 2 The full matrix least squares method was used to refine the coordinates of all atoms and the anisotropic thermal parameters. The single crystal X-ray diffraction results showed that the chemical formula of the crystals obtained in Examples 2 to 3 was C(NH 2 ) 3 H 2 PO 3 .

[0063] The phases prepared in Examples 1-6 were analyzed by powder X-ray diffraction. The powder X-ray diffraction was performed on a Rigaku Miniflex II X-ray powder diffractometer. The test conditions were a fixed target monochromatic light source Cu-Kα, a wavelength of The scanning range is 5-60°, and the scanning step is 0.02°. The powder X-ray diffraction spectrum shows that the diffraction peak positions of the samples in Examples 1-6 are basically the same. This shows that the C(NH 2 ) 3 H 2 PO 3 The single crystal structure analysis is correct and the sample is relatively pure. Figure 2 This is a comparison chart of the X-ray diffraction simulation spectrum obtained by fitting the crystal structure of the sample in Example 2 according to the single crystal X-ray diffraction data and the powder X-ray diffraction of the sample in Example 2.

[0064] Example 8C (NH 2 ) 3 H 2 PO 3 Crystal frequency doubling test experiment

[0065] like Figure 3 As shown, the C(NH 2 )3 H 2 PO 3 The frequency doubling test experiment was carried out on the crystal sample. The 1064 nm laser emitted by a Nd:YAG solid laser was used as the fundamental frequency light to irradiate the C(NH 2 ) 3 H 2 PO 3 crystal powder, and a photomultiplier tube was used to detect the generated frequency doubling light, and an oscilloscope was used to display the harmonic intensity. The specific method is as follows:

[0066] The particle size of the crystal sample to be measured was sieved into 25 - 45 μm, 45 - 62 μm, 62 - 75 μm, 75 - 109 μm, 109 - 150 μm, 150 - 212 μm, and 212 - 250 μm by a standard sieve. The crystal samples to be measured with the above particle sizes were placed at position 3 in the device shown in Figure 3 . At room temperature, a Q-switched Nd:YAG laser was used as the input light source (i.e., laser 1), the incident wavelength of the incident laser beam 2 was 1064 nm. After the incident laser beam 2 passed through the crystal 3 of Example 2, the frequency doubling signal of the output laser beam 4 after passing through the filter 5 was measured respectively, and the change trend of the frequency doubling signal with the particle size was observed to judge whether phase matching could be achieved. Under the same test conditions, KH 2 PO 4 (KDP) was used as a reference for the second harmonic generation test. The test results are as shown in Figure 4 . Figure 4 The results in it show that: C(NH 2 ) 3 H 2 PO 3 crystal (GPO) outputs strong 532 nm light under the irradiation of 1064 nm laser, and its powder frequency doubling effect is about 1.6 times that of KDP under the same conditions, and phase matching can be achieved.

[0067] Example 9 C(NH 2 ) 3 H 2 PO 3 Spectral performance test of the crystal

[0068] The ultraviolet transmission spectrum test of the C(NH 2 ) 3 H 2 PO 3 crystal sample prepared in Example 2 was carried out on a Perkin-Elmer Lambda-950 ultraviolet-visible-near-infrared spectrophotometer in the United States, and the infrared spectrum test was carried out on a Bruker VERTEX 70 infrared spectrometer. Among them, the wafer of Example 2 was polished for the transmission spectrum test. As shown in Figure 5 and Figure 6 are respectively C(NH 2 ) 3 H 2 PO 3 The UV-visible-near infrared transmission spectrum and infrared spectrum of the crystal sample show that the C(NH 2 ) 3 H 2 PO 3 It has a wide light transmittance range (200-1400nm) and a very high transmittance (>80%), and its ultraviolet absorption cut-off wavelength can reach 200nm.

[0069] Figure 7 This is a crystal photograph of Example 5. The crystal size is approximately 2.3×1.3×0.6 cm.

[0070] The above is an exemplary description of the embodiments of the present invention. However, the protection scope of the present invention is not limited to the above embodiments. Any modification, equivalent substitution, improvement, etc. made by those skilled in the art within the spirit and principle of the present invention shall be included in the protection scope of the present invention.

Claims

1. A compound, characterized in that Its chemical formula is C(NH2)3H2PO3.

2. The method for preparing the compound according to claim 1, characterized in that: The method comprises: mixing a C(NH2)3-containing compound and a P-containing compound in a solvent for reaction to prepare the compound.

3. The method according to claim 2, characterized in that The C(NH2)3-containing compound is selected from at least one of [C(NH2)3]2CO3, C(NH2)3HCO3, C(NH2)3Cl, C(NH2)3NO3 or C(NH2)3H2PO4. Preferably, the P-containing compound is selected from at least one of H3PO3, KH2PO3 and H3PO2.

4. The method according to claim 2, characterized in that: The mass volume ratio of the sum of the mass of the C(NH2)3-containing compound and the P-containing compound to the mass volume of the solvent is (10-90) g:100 mL.

5. The method according to claim 2, characterized in that: The reaction temperature is 20-95° C. and the reaction time is 5-30 days. Preferably, the method further comprises cooling the reaction solution after the mixed reaction, for example, at a cooling rate of 0.5 to 20° C. / h.

6. A nonlinear optical crystal, characterized in that: The chemical formula of the crystal is C(NH2)3H2PO3 as described in claim 1, that is, the nonlinear optical crystal is C(NH2)3H2PO3 crystal.

7. The crystal according to claim 6, characterized in that The nonlinear optical crystal belongs to the monoclinic system, the space group is P21, and the unit cell parameters are α=γ=90°, β=100.639(16)°, Z=2. Preferably, the nonlinear optical crystal is composed of [C(NH2)3] + and [H2PO3] - They are connected to each other by hydrogen bonds.

8. The method for preparing the crystal according to claim 6 or 7, characterized in that: The method comprises: The C(NH2)3-containing compound and the P-containing compound are mixed and reacted in a solvent, and heated and evaporated to obtain the crystal.

9. The method according to claim 8, characterized in that The preparation method further comprises: cooling the reaction liquid after heating and evaporation. Preferably, the cooling rate is 0.5-10°C / h.

10. Application of the crystal according to claim 6 or 7 in the fields of laser frequency doubling, electro-optic modulation, photorefractive information processing or information storage; preferably, used as a frequency doubling device in an all-solid-state laser.

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