KF [SO2 (NH2)] 2 compound and crystal, preparation method and application thereof

Abstract

The invention discloses a KF [SO2 (NH2)] 2 compound and a crystal, a preparation method and application thereof, the crystal is a KF [SO2 (NH2)] 2 crystal, the KF [SO2 (NH2)] 2 crystal outputs strong 532 nm light (double frequency) under 1064 nm laser irradiation, the powder frequency-doubled effect of the KF [SO2 (NH2)] 2 crystal is about 2.4 times that of KH2PO4 (KDP), and phase matching can be achieved. Stronger 266nm light (namely quadruplicated frequency) is output under the irradiation of 532nm laser, the powder frequency-doubled effect is 0.4 times that of BBO, and phase matching can be realized.

Description

Technical Field

[0001] The present invention belongs to the technical field of functional crystal materials, and specifically relates to a KF·[SO 2 (NH 2 )] 2 Compound and crystal thereof, preparation method and use in nonlinear optics. Background Art

[0002] With the development of all-solid-state laser technology in the fields of optical communication, optical processing and optical storage, ultraviolet nonlinear optical crystal materials have become a research hotspot at home and abroad. The ultraviolet nonlinear optical crystals that have been commercialized mainly include β-BaB 2 O 4 (abbreviated as BBO), LiB 3 O 5 (abbreviated as LBO), KBe 2 BO 3 F 2 (abbreviated as KBBF), CsB 3 O 5 (abbreviated as CBO) and CsLiB 6 O 10 (abbreviated as CLBO), etc. Among them, the KBBF family crystal is the third Chinese brand nonlinear optical crystal in the field of nonlinear optical crystal research in my country after the discovery of BBO and LBO crystals. It has a pioneering role in promoting the development and application of all-solid-state deep ultraviolet laser sources, and fully proves that my country continues to maintain an international leading level in the field of nonlinear optical crystals. With the development of laser technology, more and higher requirements have been put forward for the physical and chemical properties of nonlinear optical materials.

[0003] Nonlinear optical crystal materials require a strict non-centrosymmetric structure, so the design and preparation of materials are quite challenging. From the large number of UV / deep UV nonlinear optical crystals that have been reported, crystals that can simultaneously have a large band gap, frequency doubling coefficient, and birefringence are very rare. Therefore, exploring new UV / deep UV nonlinear optical crystals with excellent comprehensive performance is still an urgent and challenging task. Summary of the invention

[0004] In order to solve the above technical problems, the present invention provides a chemical formula KF·[SO 2 (NH 2 )] 2 of compounds.

[0005] The present invention also provides the above chemical formula KF·[SO 2 (NH 2 )] 2 A method for preparing a compound, the method comprising:

[0006] Compounds containing K, F, and [SO 2 (NH 2 )] 2 The compounds are mixed and reacted to obtain the compound.

[0007] Preferably, the K-containing compound is selected from K 2 CO 3 , KOH, K 2 SO 4 , KF, KCl or KBr, preferably KF.

[0008] Preferably, the F-containing compound is selected from one or more of KF, LiF, NaF, RbF, and CsF, preferably KF.

[0009] Preferably, the 2 (NH 2 )] 2 The compound is selected from [SO 2 (NH 2 )] 2 .

[0010] Preferably, when both the K-containing compound and the F-containing compound are KF, the KF and the compound containing [SO 2 (NH 2 )] 2 The molar ratio of the compounds is (1-10):(1-10); preferably (1-5):(1-5); illustratively 1:1.

[0011] Preferably, the reaction temperature of the reaction may be 20 to 80°C.

[0012] Preferably, the reaction time of the reaction may be 2-15 days, such as 3-13 days, illustratively 3, 5, 7, 9, 11, 12 or 13 days.

[0013] According to an embodiment of the present invention, the method is carried out in a solvent, such as water. The content of water is not particularly limited, as long as it can dissolve the raw materials.

[0014] In the present invention, KF·[SO 2 (NH 2 )] 2 The compounds usually exist in crystalline form.

[0015] The present invention also provides a nonlinear optical crystal, the chemical formula of which is KF·[SO 2 (NH 2 )] 2 , that is, the nonlinear optical crystal is KF·[SO2 (NH 2 )] 2 Crystal.

[0016] According to an embodiment of the present invention, the nonlinear optical crystal belongs to the tetragonal system, and the space group is The unit cell parameters are α=γ=β=90°, z=2.

[0017] Preferably, the nonlinear optical crystal has Figure 2 X-ray diffraction pattern shown.

[0018] According to one embodiment of the present invention, the structural schematic diagram of the nonlinear optical crystal is as follows: Figure 1 As shown, the crystal consists of polar tetrahedron [SO 2 (NH 2 )] 2 As a basic building block, each [SO 2 (NH 2 ) 2 ] is connected to the linear KF through KO bonds and NH···F hydrogen bonds ( Figure 1 a), forming a layer perpendicular to the c direction ( Figure 1 b), and along the c direction, the adjacent [SO 2 (NH 2 ) 2 ] layer shows an arrangement with a 90 degree turn.

[0019] The present invention also provides a method for preparing the nonlinear optical crystal, which comprises:

[0020] Compounds containing K, F, and [SO 2 (NH 2 )] 2 The compounds are mixed and reacted to obtain the crystals.

[0021] Preferably, the K-containing compound is selected from K 2 CO 3 , KOH, K 2 SO 4 , KF, KCl or KBr, preferably KF.

[0022] Preferably, the F-containing compound is selected from one or more of KF, LiF, NaF, RbF, and CsF, preferably KF.

[0023] Preferably, the 2 (NH 2 )] 2 The compound is selected from [SO2 (NH 2 )] 2 .

[0024] Preferably, when both the K-containing compound and the F-containing compound are KF, KF and [SO 2 (NH 2 )] 2 The molar ratio is (1-10):(1-10); preferably (1-5):(1-5); illustratively 1:1.

[0025] Preferably, the reaction temperature of the reaction may be 20 to 80°C.

[0026] Preferably, the reaction time of the reaction may be 2-15 days, such as 3-13 days, illustratively 3, 5, 7, 9, 11, 12 or 13 days.

[0027] According to an embodiment of the present invention, the method is carried out in a solvent, such as water. The content of water is not particularly limited, as long as it can dissolve the raw materials.

[0028] As an exemplary embodiment of the present invention, the method specifically comprises the following steps:

[0029] Compounds containing K, F, and [SO 2 (NH 2 )] 2 After the compound and water are mixed, an evaporation reaction is performed to obtain the crystals.

[0030] The present invention also provides applications of the nonlinear optical crystal, which can be used in the fields of nonlinear optics, laser technology, electro-optic modulation, photorefractive information processing, etc.

[0031] Preferably, the nonlinear optical crystal can be used in a frequency doubling generator.

[0032] Preferably, the frequency doubling generator is used in deep ultraviolet and ultraviolet bands.

[0033] Beneficial effects of the present invention:

[0034] (1) KF·[SO of the present invention 2 (NH 2 )] 2 The crystal outputs strong 532nm light (i.e. double frequency) under 1064nm laser irradiation, and its powder double frequency effect is about KH 2 PO 4 Under 532nm laser irradiation, it outputs strong 266nm light (i.e., frequency quadrupling), and its powder frequency doubling effect is 0.4 times that of BBO, and phase matching can be achieved.

[0035] (2) KF·[SO of the present invention 2 (NH 2 )] 2 The crystal has a wide light transmission range, with high transmittance between 190-2200nm, ultraviolet cutoff edge <190nm, and moderate birefringence at 1064nm, which is 0.07. It can be applied to the short-wave ultraviolet region and even the deep ultraviolet band, and has potential application prospects in the fields of nonlinear optics, laser technology, electro-optic modulation, photorefractive information processing, etc.

[0036] (3) KF·[SO of the present invention 2 (NH 2 )] 2 The preparation method of the compound and the crystal has simple process, fast growth speed and low cost. BRIEF DESCRIPTION OF THE DRAWINGS

[0037] Figure 1 KF·[SO 2 (NH 2 )] 2 Schematic diagram of the crystal structure of the crystal, where 1a is a schematic diagram of the overall structure of the crystal; 1b is a schematic diagram of the crystal structure along the c-axis direction. 2 (NH 2 )] 2 Schematic diagram of the arrangement of groups.

[0038] Figure 2 This is a comparison chart of the X-ray diffraction simulation spectrum obtained by fitting the crystal structure of the sample obtained in Example 2 according to the single crystal X-ray diffraction data and the powder X-ray diffraction of the sample obtained in Example 2.

[0039] Figure 3 This is the UV transmittance spectrum of the sample obtained in Example 2.

[0040] Figure 4 is the KF·[SO obtained in Example 2 2 (H 2 )] 2 Schematic diagram of the nonlinear optical effect when the crystal is used as a frequency doubling crystal, where 1 is the laser, 2 is the incident laser beam, and 3 is the KF·[SO 2 (NH 2 )] 2 Nonlinear optical crystal, 4 is the generated laser beam, 5 is the photomultiplier tube equipped with a filter.

[0041] Figure 5 is the KF·[SO obtained in Example 2 2 (NH 2 )] 2 Frequency doubling test results of crystal samples. DETAILED DESCRIPTION

[0042] 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.

[0043] Unless otherwise specified, the raw materials and reagents used in the following examples are commercially available or can be prepared by known methods.

[0044] Example 1

[0045] KF·[SO 2 (NH 2 )] 2 Crystal preparation

[0046] KF·[SO 2 (NH 2 )] 2 Crystal:

[0047] (a) KF (0.01 mol, 0.581 g) and [SO 2 (NH 2 )] 2 (0.01 mol, 0.961 g) was placed in a glass beaker and 20 mL of deionized water was added, and the mixture was evaporated at 35 °C for 10 days;

[0048] (b) After evaporation, the resulting crystals can be separated and dried to obtain KF·[SO 2 (NH 2 )] 2 Crystal.

[0049] Example 2

[0050] KF·[SO 2 (NH 2 )] 2 Crystal preparation

[0051] KF·[SO 2 (NH 2 )] 2 Crystal:

[0052] (a) KF (0.01 mol, 0.581 g) and [SO 2 (NH 2 )] 2 (0.01 mol, 0.961 g) was placed in a glass beaker and 20 mL of deionized water was added, and the mixture was evaporated at 45 °C for 7 days;

[0053] (b) After evaporation, the resulting crystals can be separated and dried to obtain KF·[SO 2 (NH 2 )] 2 Crystal.

[0054] Example 3

[0055] KF·[SO 2 (NH 2 )] 2 Crystal preparation

[0056] KF·[SO 2 (NH 2 )] 2 Crystal:

[0057] (a) KF (0.01 mol, 0.581 g) and [SO 2 (NH 2 )] 2 (0.01 mol, 0.961 g) was placed in a glass beaker and 20 mL of deionized water was added, and the mixture was evaporated at 55 °C for 4 days;

[0058] (b) After evaporation, the resulting crystals can be separated and dried to obtain KF·[SO 2 (NH 2 )] 2 Crystal.

[0059] Example 4

[0060] KF·[SO 2 (NH 2 )] 2 Crystal structure analysis

[0061] The KF·[SO 2 (NH 2 )] 2 The crystal samples were subjected to structural analysis. The single crystal X-ray diffraction results showed that the chemical formulas of the samples in Examples 1-3 were all KF·[SO 2 (NH 2 )] 2 , belongs to the tetragonal system, and its structural diagram is shown in Figure 1 As shown, the space group is The unit cell parameters are α=γ=β=90°, z=2.

[0062] The powder X-ray diffraction spectrum shows that the diffraction peak positions of the samples in Examples 1 to 3 are substantially the same. Taking the sample in Example 2 as a typical representative, its powder X-ray diffraction spectrum result is as follows: Figure 2 shown. Figure 2 The results show that the X-ray diffraction pattern obtained by fitting the crystal structure analyzed by single crystal X-ray diffraction is consistent with the KF·[SO 2 (NH 2 )] 2 The peak positions and peak intensities of the powder X-ray diffraction patterns of the crystalline samples are consistent.

[0063] Example 5

[0064] KF·[SO 2 (NH 2 )] 2 Crystal frequency doubling test experiment

[0065] The KF·[SO 2 (NH 2 )] 2 The crystal sample was subjected to frequency doubling test experiment, and the KF·[SO 2 (NH 2 )] 2 When the crystal is used as a frequency doubling crystal, a typical schematic diagram of the nonlinear optical effect is shown in the figure below: Figure 4 As shown, 1 is the laser, 2 is the incident laser beam, and 3 is KF·[SO 2 (NH 2 )] 2 Nonlinear optical crystal, 4 is the generated laser beam, 5 is the photomultiplier tube equipped with a filter.

[0066] The 1064nm laser emitted by Nd:YAG solid laser and the 532nm laser obtained by frequency conversion using BBO crystal were used as fundamental frequency light to irradiate the tested crystal powder, and the generated double frequency light was detected by photomultiplier tube, and the harmonic intensity was displayed by oscilloscope. The particle size of the crystal sample to be tested was sieved into 25-45μm, 45-62μm, 62-75μm, 75-109μm, 109-150μm and 150-212μm by standard sieve, and the double frequency signal was tested respectively, and the change trend of the double frequency signal with the particle size was observed to determine whether it can achieve phase matching. Under the same test conditions, KH 2 PO 4 (KDP) and BBO were used as reference materials for double frequency and quadruple frequency tests. Figure 5 As shown, the test results show that: KF·[SO 2 (NH 2 )] 2Under 1064nm laser irradiation, the powder frequency-doubled effect of the crystal is 2.4 times that of KDP, and phase matching can be achieved; under 532nm laser irradiation, the powder frequency-doubled effect of the crystal is 0.4 times that of BBO.

[0067] Example 6

[0068] KF·[SO 2 (NH 2 )] 2 Crystal spectral performance test

[0069] The KF·[SO 2 (NH 2 )] 2 Taking the crystal sample as a representative, the spectral performance test from ultraviolet to infrared was carried out.

[0070] The UV transmission spectrum test was performed on a UV-Vis-NIR spectrophotometer. The test results are as follows Figure 3 As shown, Figure 3 The results show that KF·[SO 2 (NH 2 )] 2 The crystal has a wide transmission range, with high transmittance in the spectral range of 190-2000nm, and the ultraviolet absorption cut-off wavelength is <190nm; and the birefringence at 1064nm is moderate, which is 0.07.

[0071] 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 KF·[SO2(NH2)]2.

2. The method for preparing the compound according to claim 1, characterized in that: The method comprises: A K-containing compound, a F-containing compound and a [SO2(NH2)]2-containing compound are mixed and reacted to obtain the compound.

3. The method according to claim 2, characterized in that The K-containing compound is selected from one or more of K2CO3, KOH, K2SO4, KF, KCl or KBr. Preferably, the F-containing compound is selected from one or more of KF, LiF, NaF, RbF, and CsF. Preferably, the [SO2(NH2)]2-containing compound is selected from [SO2(NH2)]2.

4. The method according to claim 2, characterized in that: When both the K-containing compound and the F-containing compound are KF, the molar ratio of KF to the [SO2(NH2)]2-containing compound is (1-10):(1-10). Preferably, the reaction temperature of the reaction is 20-80° C.; the reaction time of the reaction is 2-15 days.

5. The method according to claim 2, characterized in that: The reaction is carried out in a solvent.

6. A nonlinear optical crystal, characterized in that: The chemical formula of the crystal is KF·[SO2(NH2)]2 as stated in claim 1, that is, the nonlinear optical crystal is KF·[SO2(NH2)]2 crystal.

7. The crystal according to claim 6, characterized in that The nonlinear optical crystal belongs to the tetragonal system, and the space group is The unit cell parameters are α=γ=β=90°, z=2.

8. The crystal according to claim 6, characterized in that The schematic diagram of the structure of the nonlinear optical crystal is shown in Figure 1. The crystal is composed of polar tetrahedral [SO2(NH2)]2 groups as basic building units. Each [SO2(NH2)2] is connected to the linear KF through a KO bond and an NH···F hydrogen bond to form a layer perpendicular to the c direction, and along the c direction, adjacent [SO2(NH2)2] layers show an arrangement with a rotation angle of 90 degrees.

9. The method for preparing the crystal according to any one of claims 6 to 8, characterized in that: The method is: A K-containing compound, a F-containing compound, and a [SO2(NH2)]2-containing compound are mixed and reacted to obtain the crystal.

10. Use of the crystal according to any one of claims 6 to 8, characterized in that: It is used in the fields of nonlinear optics, laser technology, electro-optic modulation or photorefractive information processing. Preferably, the nonlinear optical crystal is used in a frequency doubling generator. Preferably, the frequency doubling generator is used in deep ultraviolet and ultraviolet bands.

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