A nonlinear optical crystal of aminoguanidine hydroxyphosphite and its preparation method and use

Abstract

The present invention provides a nonlinear optical crystal of aminoguanidine hydroxyphosphite, a preparation method and an application thereof. The chemical formula of the crystal compound is [CN4H7]HPO2(OH), the molecular weight is 156.09, it belongs to the orthorhombic crystal system, and the space group is Pna 21, the unit cell parameters are a =14.9947(10)Å, b =6.5890(4)Å, c =6.6691(4)Å, α = 90°, β= 90°, γ= 90°, unit cell volume is 658.91(7)Å 3 The frequency doubling effect of the crystal is about 0.5 times that of KH2PO4 (KDP), and the ultraviolet cutoff edge is about 196nm. The crystal is grown by evaporation, hydrothermal or room temperature solution method. The crystal has good chemical stability and can be used as a short-wavelength ultraviolet nonlinear optical crystal in all-solid-state lasers.

Description

Technical Field

[0001] The present invention relates to a hydroxyaminoguanidine phosphite [CN4H7]HPO2(OH) nonlinear optical crystal, a preparation method and application thereof. Background Art

[0002] Short-wavelength nonlinear optical crystals can utilize their frequency conversion properties to convert lasers in near-infrared and visible bands into short-wavelength lasers, offering important applications in fields such as medicine, communications, and scientific research. Currently, Chinese-made short-wavelength nonlinear optical crystals include KBe2BO3F2 (KBBF), BaB2O4 (BBO), and LiB3O5 (LBO). However, these crystals suffer from limitations such as low birefringence and difficulty growing large crystals, which limit their applications. Therefore, the preparation and synthesis of novel short-wavelength nonlinear optical crystal materials with superior overall performance is of great significance and practical value.

[0003] When designing and developing new short-wavelength nonlinear optical crystals, people hope to obtain crystals with large second-order nonlinear coefficients, wide transmittance range, short cutoff edge, and moderate birefringence. Summary of the Invention

[0004] The present invention aims to provide a nonlinear optical crystal of aminoguanidine hydroxyphosphite, the chemical formula of the crystal is [CN4H7]HPO2(OH), the molecular weight is 156.09, it belongs to the orthorhombic crystal system, the space group is Pna21, and the unit cell parameters are α=90°,β=90°,γ=90°, the unit cell volume is

[0005] Another object of the present invention is to provide a method for preparing hydroxyaminoguanidine phosphite nonlinear optical crystals, wherein the crystals are grown by evaporation, hydrothermal or room temperature solution method.

[0006] Another object of the present invention is to provide a use of hydroxyaminoguanidine phosphite [CN4H7]HPO2(OH) nonlinear optical crystal.

[0007] The present invention relates to a nonlinear optical crystal of aminoguanidine hydroxyphosphite, the chemical formula of which is [CN4H7]HPO2(OH), the molecular weight is 156.09, belongs to the orthorhombic crystal system, the space group is Pna21, and the unit cell parameters are α=90°,β=90°,γ=90°, the unit cell volume is It is made by evaporation method, hydrothermal method and room temperature solution method.

[0008] The method for preparing the hydroxyaminoguanidine phosphite nonlinear optical crystal adopts an evaporation method, a hydrothermal method or a room temperature solution method to grow the crystal.

[0009] The evaporation method for growing hydroxyaminoguanidine phosphite crystals is specifically performed in the following steps:

[0010] a. Mix the compound containing [CN4H7] and the compound containing P in a molar ratio of [CN4H7]:P=1:1, add 0-80 ml of deionized water to mix, and obtain a mixed solution, and then treat it with ultrasound to fully mix and dissolve it to obtain a clear solution; the compound containing [CN4H7] is CN4H7Cl, CN4H8CO3, CN4H7NO3 or CN4H8SO4; the compound containing P is H3PO3 and K2HPO3;

[0011] b. placing the clarified solution in step a in a resistance furnace, heating it to 50-85° C. at a rate of 10-20° C. / h, and standing at the constant temperature for 6-15 days to evaporate the solvent. After crystal growth is completed, hydroxyaminoguanidine phosphite nonlinear optical crystals are obtained;

[0012] The hydrothermal method for growing aminoguanidine hydroxyphosphite crystals is specifically performed in the following steps:

[0013] a. Mix the compound containing [CN4H7] and the compound containing P in a molar ratio of [CN4H7]:P=1:1, add 0-40 ml of deionized water to fully mix and dissolve them to obtain a mixed solution, wherein the compound containing [CN4H7] is CN4H7Cl, CN4H8CO3, CN4H7NO3 or CN4H8SO4; the compound containing P is H3PO3 and K2HPO3;

[0014] b. Transferring the mixed solution from step a into a polytetrafluoroethylene liner of a hydrothermal reactor with a volume of 23-100 ml, and tightening and sealing the reactor; then heating the mixture to 180-200° C. at a rate of 10-20° C. / h, keeping the temperature constant for 2-5 days, and then cooling the mixture to room temperature at a rate of 1-2° C. / h to obtain a hydroxyaminoguanidine phosphite nonlinear optical crystal;

[0015] The room temperature solution method for growing hydroxyaminoguanidine phosphite crystals is specifically performed according to the following steps:

[0016] a. Mix the compound containing [CN4H7] and the compound containing P in a molar ratio of [CN4H7]:P=1:1, add 50-150 ml of deionized water to fully mix and dissolve them to obtain a mixed solution, wherein the compound containing [CN4H7] is CN4H7Cl, CN4H8CO3, CN4H7NO3 or CN4H8SO4; the compound containing P is H3PO3 and K2HPO3;

[0017] b. Ultrasonic treatment is performed on the mixed solution in step a to fully dissolve it to obtain a clear solution. The container is tightly sealed with a polyvinyl chloride film and placed in a static environment without shaking, pollution, or air convection. Several small holes are punched in the sealing film and the solution is allowed to stand at room temperature for 10-20 days. Subsequently, crystals in the solution precipitate and gradually grow, thereby obtaining hydroxyaminoguanidine phosphite nonlinear optical crystals.

[0018] The hydroxyaminoguanidine phosphite nonlinear optical crystal is used in preparing harmonic light output of 2-, 3-, 4- and 5-fold frequency of 1064nm fundamental frequency light output by an Nd:YAG laser.

[0019] The hydroxyaminoguanidine phosphite nonlinear optical crystal is used in preparing ultraviolet frequency-doubled light output below 213 nm.

[0020] The hydroxyaminoguanidine phosphite nonlinear optical crystal is used in preparing a frequency doubling generator, an up- or down-frequency converter or an optical parametric oscillator.

[0021] The present invention discloses a method for preparing a nonlinear optical crystal of aminoguanidine hydroxyphosphite. The preparation process utilizes a polytetrafluoroethylene beaker lined with polytetrafluoroethylene and a stainless steel-lined hydrothermal kettle equipped with a platinum sleeve. Before use, the container must be cleaned with acid, rinsed with deionized water, and air-dried. The resistance furnace used in the preparation process is a muffle furnace or drying oven.

[0022] The hydroxyaminoguanidine phosphite nonlinear optical crystal obtained by the method of the present invention has a centimeter-scale [CN4H7]HPO2(OH) nonlinear optical crystal. By using a large-sized container and extending the crystal growth period, a corresponding large-sized nonlinear optical crystal [CN4H7]HPO2(OH) can be obtained. During the growth of the [CN4H7]HPO2(OH) nonlinear optical crystal, the crystal is easy to grow, transparent and without wrapping, and has the advantages of fast growth speed, low cost, and easy acquisition of large-sized crystals.

[0023] The hydroxyaminoguanidine phosphite nonlinear optical crystal obtained by the method of the present invention can be used as a nonlinear optical device by orienting the crystal blank according to the crystallographic data of the crystal, cutting the crystal according to the required angle, thickness and cross-sectional size, and polishing the light-transmitting surface of the crystal. The [CN4H7]HPO2(OH) nonlinear optical crystal has the advantages of a wide light transmission band, stable physical and chemical properties, and easy processing and storage. BRIEF DESCRIPTION OF THE DRAWINGS

[0024] Figure 1 The powder XRD spectrum of the compound [CN4H7]HPO2(OH) of the present invention is shown in FIG.

[0025] Figure 2 This is a structural diagram of the [CN4H7]HPO2(OH) crystal of the present invention;

[0026] Figure 3 This is a working principle diagram of the nonlinear optical device made of [CN4H7]HPO2(OH) crystal of the present invention, where 1 is the laser, 2 is the emitted light beam, 3 is the [CN4H7]HPO2(OH) crystal, 4 is the output light beam, and 5 is the filter. DETAILED DESCRIPTION

[0027] The present invention is further described below with reference to the following examples. It should be noted that the following examples are not intended to limit the scope of the present invention, and any improvements made based on the present invention do not violate the spirit of the present invention. Unless otherwise specified, the raw materials and equipment used in the present invention are commercially available.

[0028] Example 1

[0029] According to the reaction formula: CN4H7Cl+H3PO3→[CN4H7]HPO2(OH)+HCl, the [CN4H7]HPO2(OH) nonlinear optical crystal is grown by evaporation method:

[0030] a. Mix CN4H7Cl and H3PO3 in a molar ratio of 1:1, place in a 100ml polytetrafluoroethylene beaker, add 80ml of deionized water, stir to obtain a mixed solution; then treat with ultrasound to fully mix and dissolve to obtain a clear solution;

[0031] b. Place the clarified solution in step a in a resistance furnace, raise the temperature to 85°C at a rate of 20°C / h, and keep it at this temperature for 8 days to evaporate the solvent. After the crystal growth is completed, a hydroxyaminoguanidine phosphite nonlinear optical crystal with a size of Φ4 mm × 3 mm × 1.6 mm is obtained.

[0032] Example 2

[0033] According to the reaction formula: CN4H8CO3+H3PO3→[CN4H7]HPO2(OH)+CO2+H2O, the [CN4H7]HPO2(OH) nonlinear optical crystal is grown by evaporation method:

[0034] a. Mix CN4H8CO3 and H3PO3 in a molar ratio of 1:1, place in a 200ml polytetrafluoroethylene beaker, add 60ml deionized water, stir evenly to obtain a mixed solution, and then treat with ultrasound to fully mix and dissolve to obtain a clear solution;

[0035] b. Place the clarified solution in step a in a resistance furnace, raise the temperature to 75°C at a rate of 15°C / h, and keep it at this temperature for 10 days to evaporate the solvent. After crystal growth is completed, a hydroxyaminoguanidine phosphite nonlinear optical crystal with a size of Φ5 mm × 2 mm × 1.1 mm is obtained.

[0036] Example 3

[0037] According to the reaction formula: CN4H7NO3+H3PO3→[CN4H7]HPO2(OH)+NO2+H2O, the [CN4H7]HPO2(OH) nonlinear optical crystal is grown by evaporation method:

[0038] a. Mix CN4H7NO3 and H3PO3 in a molar ratio of 1:1, place in a 300ml polytetrafluoroethylene beaker, add 50ml of deionized water, stir evenly to obtain a mixed solution, and then treat with ultrasound to fully mix and dissolve to obtain a clear solution;

[0039] b. Place the mixed solution in step a in a resistance furnace, heat it to 50°C at a rate of 10°C / h, keep it at this temperature for 15 days, evaporate the solvent, and wait for the crystal growth to complete to obtain a hydroxyaminoguanidine phosphite nonlinear optical crystal with a size of Φ3 mm × 1.3 mm × 0.6 mm.

[0040] Example 4

[0041] According to the reaction formula: CN4H7NO3+KH2PO3→[CN4H7]HPO2(OH)+KNO3, [CN4H7]HPO2(OH) nonlinear optical crystal is grown by evaporation method:

[0042] a. Mix CN4H7NO3 and KH2PO3 in a molar ratio of 1:1, place in a 50ml polytetrafluoroethylene beaker, add 40ml deionized water and mix evenly, then treat with ultrasound to fully mix and dissolve to obtain a clear solution;

[0043] b. Place the mixed solution in step a in a resistance furnace, raise the temperature to 55° C. at a rate of 12° C. / h, and keep the temperature constant for 8 days to evaporate the solvent. After crystal growth is completed, a hydroxyaminoguanidine phosphite nonlinear optical crystal with a size of Φ6 mm×4.3 mm×2.1 mm is obtained;

[0044] Example 5

[0045] According to the reaction formula: CN4H8SO4+KH2PO3→[CN4H7]HPO2(OH)+KHSO4, [CN4H7]HPO2(OH) nonlinear optical crystal is grown by evaporation method:

[0046] a. Place CN4H8SO4 and KH2PO3 in a 150ml polytetrafluoroethylene beaker in a molar ratio of 1:1 and mix well. Add 70ml of deionized water and stir well to obtain a mixed solution. Then, treat with ultrasound to ensure that the mixture is fully mixed and dissolved to obtain a clear solution.

[0047] b. Place the clarified solution from step a in a resistance furnace, raise the temperature to 75°C at a rate of 20°C / h, and maintain the temperature for 15 days to evaporate the solvent. Crystals precipitate and gradually grow. When crystal growth is complete, a [CN4H7]HPO2(OH) nonlinear optical crystal with a size of Φ5 mm × 3.1 mm × 1.3 mm is obtained.

[0048] Example 6

[0049] According to the reaction formula: CN4H7NO3+H3PO3→[CN4H7]HPO2(OH)+NO2+H2O, the [CN4H7]HPO2(OH) nonlinear optical crystal is grown by hydrothermal method:

[0050] a. Mix CN4H7NO3 and H3PO3 in a molar ratio of 1:1, add the mixture into a polytetrafluoroethylene liner of a 100 ml hydrothermal reactor, add 40 ml of deionized water, and stir to obtain a mixed solution;

[0051] b. Place the reactor in step a in a constant temperature box, raise the temperature to 180°C at a rate of 15°C / h, maintain the temperature for 2 days, then cool it to room temperature at a rate of 1°C / h, open the high-pressure reactor, and obtain a [CN4H7]HPO2(OH) nonlinear optical crystal with a size of 2 mm × 1.3 mm × 0.5 mm.

[0052] Example 7

[0053] According to the reaction formula: CN4H7Cl+H3PO3→[CN4H7]HPO2(OH)+HCl, the [CN4H7]HPO2(OH) nonlinear optical crystal is grown by hydrothermal method:

[0054] a. Mix CN4H7Cl and H3PO3 in a molar ratio of 1:1, add 15 ml of deionized water, and stir to obtain a mixed solution;

[0055] b. Transfer the mixed solution in step a into the polytetrafluoroethylene liner of a 23 ml hydrothermal reactor, and tighten and seal the reactor; place the reactor in a constant temperature box, raise the temperature to 190° C. at a rate of 15° C. / h, keep the temperature constant for 2 days, then cool it to room temperature at a rate of 1° C. / h, open the high-pressure reactor, and obtain a [CN4H7]HPO2(OH) nonlinear optical crystal with a size of 1.3 mm × 0.6 mm × 0.3 mm.

[0056] Example 8

[0057] According to the reaction formula: CN4H8SO4+KH2PO3→[CN4H7]HPO2(OH)+KHSO4, the [CN4H7]HPO2(OH) nonlinear optical crystal is grown by hydrothermal method:

[0058] a. Mix CN4H8SO4 and K2HPO3 in a molar ratio of 1:1, add 30 ml of deionized water, and stir to obtain a mixed solution;

[0059] b. Transfer the mixed solution in step a into the polytetrafluoroethylene liner of a 100 ml hydrothermal reactor, tighten and seal the reactor, place the reactor in a constant temperature box, raise the temperature to 200°C at a rate of 20°C / h, keep the temperature constant for 5 days, then cool to room temperature at a rate of 1°C / h, open the high-pressure reactor, and obtain a [CN4H7]HPO2(OH) nonlinear optical crystal with a size of 2.4 mm × 1.3 mm × 0.6 mm.

[0060] Example 9

[0061] According to the reaction formula: CN4H8CO3+H3PO3→[CN4H7]HPO2(OH)+CO2+H2O, the [CN4H7]HPO2(OH) nonlinear optical crystal is grown by hydrothermal method:

[0062] a. Mix CN4H8CO3 and H3PO3 in a molar ratio of 1:1, add 12 ml of deionized water, and stir to obtain a mixed solution;

[0063] b. Transfer the mixed solution in step a into the polytetrafluoroethylene liner of a 23 ml hydrothermal reactor, and tighten and seal the reactor; place the reactor in a constant temperature box, raise the temperature to 180° C. at a rate of 15° C. / h, keep the temperature constant for 2 days, then cool it to room temperature at a rate of 2° C. / h, open the high-pressure reactor, and a [CN4H7]HPO2(OH) nonlinear optical crystal with a size of 1.8 mm × 0.8 mm × 0.4 mm can be obtained.

[0064] Example 10

[0065] According to the reaction formula: CN4H7NO3+KH2PO3→[CN4H7]HPO2(OH)+KNO3, the [CN4H7]HPO2(OH) nonlinear optical crystal is grown by hydrothermal method:

[0066] a. Mix CN4H7NO3 and KH2PO3 in a molar ratio of 1:1, add 40 ml of deionized water, and stir to obtain a mixed solution;

[0067] b. Transfer the mixed solution in step a into the polytetrafluoroethylene liner of a 100 ml hydrothermal reactor, and tighten and seal the reactor; place the reactor in a constant temperature box, raise the temperature to 200° C. at a rate of 20° C. / h, maintain the temperature for 5 days, then cool it to room temperature at a rate of 2° C. / h, open the high-pressure reactor, and a [CN4H7]HPO2(OH) nonlinear optical crystal with a size of 4.3 mm × 1.5 mm × 0.6 mm can be obtained.

[0068] Example 11

[0069] According to the reaction formula: CN4H8CO3+H3PO3→[CN4H7]HPO2(OH)+CO2+H2O, [CN4H7]HPO2(OH) is grown by room temperature solution method:

[0070] a. Mix CN4H8CO3 and H3PO3 in a molar ratio of 1:1, add 120 ml of deionized water, and stir to obtain a mixed solution;

[0071] b. Ultrasonicate the mixed solution in step a to fully mix and dissolve it to obtain a clear solution. Seal the solution with polyvinyl chloride film and place it in a static environment without shaking, pollution, or air convection. Punch several small holes in the seal to adjust the volatilization rate of the solvent in the solution. Let it stand at room temperature for 10 days, and then crystals will gradually precipitate from the solution. After the reaction is completed, a [CN4H7]HPO2(OH) nonlinear optical crystal with a size of 9.3 mm × 4.8 mm × 2 mm can be obtained.

[0072] Example 12

[0073] According to the reaction formula: CN4H7NO3+KH2PO3→[CN4H7]HPO2(OH)+KNO3, [CN4H7]HPO2(OH) nonlinear optical crystal was grown by room temperature solution method:

[0074] a. Mix CN4H7NO3 and KH2PO3 in a molar ratio of 1:1, add 50 ml of deionized water, and stir to obtain a mixed solution;

[0075] b. Ultrasonicate the mixed solution in step a to fully mix and dissolve it to obtain a clear solution. Seal the solution with polyvinyl chloride film and place it in a static environment without shaking, pollution, or air convection. Punch a number of small holes in the seal to adjust the volatilization rate of the solvent in the solution. Let it stand at room temperature for 12 days, and then crystals will gradually precipitate from the solution. After the reaction is completed, a [CN4H7]HPO2(OH) nonlinear optical crystal with a size of 5.2 mm × 2 mm × 1.4 mm can be obtained.

[0076] Example 13

[0077] Preparation of compounds:

[0078] According to the reaction formula: CN4H7Cl+H3PO3→[CN4H7]HPO2(OH)+HCl, [CN4H7]HPO2(OH) nonlinear optical crystal was grown by room temperature solution method:

[0079] a. Mix CN4H7Cl and H3PO3 in a molar ratio of 1:1, add 70 ml of deionized water, and stir to obtain a mixed solution;

[0080] b. Ultrasonicate the mixed solution in step a to fully mix and dissolve it to obtain a clear solution. Seal the solution with polyvinyl chloride film and place it in a static environment without shaking, pollution, or air convection. Punch a number of small holes in the seal to adjust the volatilization rate of the solvent in the solution. Let it stand at room temperature for 15 days, and then crystals will gradually precipitate from the solution. After the reaction is completed, a [CN4H7]HPO2(OH) nonlinear optical crystal with a size of 6.4 mm × 4.2 mm × 2 mm can be obtained.

[0081] Example 14

[0082] According to the reaction formula: CN4H7NO3+H3PO3→[CN4H7]HPO2(OH)+NO2+H2O, [CN4H7]HPO2(OH) nonlinear optical crystal was grown by room temperature solution method:

[0083] a. Mix CN4H7NO3 and +H3PO3 in a molar ratio of 1:1, add 50 ml of deionized water, and stir to obtain a mixed solution;

[0084] b. Ultrasonicate the mixed solution in step a to fully mix and dissolve it to obtain a clear solution, then seal it with a polyvinyl chloride film and place it in a static environment without shaking, pollution, or air convection. Punch a number of small holes in the seal to adjust the volatilization rate of the solvent in the solution. Let it stand at room temperature for 20 days, then crystals gradually precipitate from the solution. After the reaction is completed, a [CN4H7]HPO2(OH) nonlinear optical crystal with a size of 2 mm × 1.6 mm × 0.4 mm can be obtained.

[0085] Example 15

[0086] According to the reaction formula: CN4H8SO4+KH2PO3→[CN4H7]HPO2(OH)+KHSO4, [CN4H7]HPO2(OH) nonlinear optical crystal was grown by room temperature solution method:

[0087] a. Mix CN4H8SO4 and KH2PO3 in a molar ratio of 1:1, add 100 ml of deionized water, and stir to obtain a mixed solution;

[0088] b. Ultrasonicate the mixed solution in step a to fully mix and dissolve it to obtain a clear solution, then seal it with a polyvinyl chloride film and place it in a static environment without shaking, pollution, or air convection. Punch a number of small holes in the seal to adjust the volatilization rate of the solvent in the solution. Let it stand at room temperature for 18 days, then gradually precipitate crystals from the solution. After the reaction is completed, a [CN4H7]HPO2(OH) nonlinear optical crystal with a size of 1.2 mm × 0.8 mm × 0.4 mm can be obtained.

[0089] Example 16

[0090] The [CN4H7]HPO2(OH) nonlinear optical crystals obtained in Examples 1-15 are processed in the matching direction. Figure 3 As shown, it is placed at position 3. At room temperature, a Q-switched Nd:YAG laser is used as the light source with an incident wavelength of 1064 nm. The infrared beam 2 with a wavelength of 1064 nm emitted by the Q-switched Nd:YAG laser 1 is incident on the [CN4H7]HPO2(OH) single crystal 3, generating green frequency-doubled light with a wavelength of 532 nm. The output intensity is about 0.5 times that of KDP under the same conditions. At the same time, under the same experimental setup, purple frequency-doubled light with a wavelength of 266 nm is generated, and the output intensity is 0.1 times that of BBO under the same conditions.

Claims

1. A nonlinear optical crystal of aminoguanidine hydroxyphosphite, characterized in that: The chemical formula of the crystal is [CN4H7]HPO2(OH), the molecular weight is 156.09, it belongs to the orthorhombic system, and the space group is Pna 21, the unit cell parameters are a =14.9947(10) Å, b =6.5890(4) Å, c =6.6691(4) Å, α= 90°, β= 90°, γ= 90°, unit cell volume is 658.91(7)Å 3 , made by evaporation method, hydrothermal method and room temperature solution method.

2. The method for preparing the nonlinear optical crystal of aminoguanidine hydroxyphosphite according to claim 1, characterized in that Growing crystals using evaporation, hydrothermal, or room temperature solution methods; The evaporation method for growing hydroxyaminoguanidine phosphite crystals is specifically performed in the following steps: a. Mix the compound containing [CN4H7] and the compound containing P in a molar ratio of [CN4H7]:P=1:1, add 0-80 ml of deionized water to mix, and obtain a mixed solution, and then treat it with ultrasound to fully mix and dissolve it to obtain a clear solution; The compound containing [CN4H7] is CN4H7Cl, CN4H8CO3, CN4H7NO3, or CN4H8SO4; the compound containing P is H3PO3 and K2HPO3; b. placing the clarified solution in step a in a resistance furnace, heating it to 50-85° C. at a rate of 10-20° C. / h, and standing at the constant temperature for 6-15 days to evaporate the solvent. After crystal growth is completed, hydroxyaminoguanidine phosphite nonlinear optical crystals are obtained; The hydrothermal method for growing aminoguanidine hydroxyphosphite crystals is specifically performed in the following steps: a. Mix the compound containing [CN4H7] and the compound containing P in a molar ratio of [CN4H7]:P=1:1, add 0-40 ml of deionized water to fully mix and dissolve them to obtain a mixed solution, wherein the compound containing [CN4H7] is CN4H7Cl, CN4H8CO3, CN4H7NO3, or CN4H8SO4; the compound containing P is H3PO3 and K2HPO3; b. Transferring the mixed solution from step a into a polytetrafluoroethylene liner of a hydrothermal reactor with a volume of 23-100 ml, and tightening and sealing the reactor; then heating the mixture to 180-200° C. at a rate of 10-20° C. / h, keeping the temperature constant for 2-5 days, and then cooling the mixture to room temperature at a rate of 1-2° C. / h to obtain a hydroxyaminoguanidine phosphite nonlinear optical crystal; The room temperature solution method for growing hydroxyaminoguanidine phosphite crystals is specifically performed according to the following steps: a. Mix the compound containing [CN4H7] and the compound containing P in a molar ratio of [CN4H7]:P=1:1, add 50-150 ml of deionized water to fully mix and dissolve them to obtain a mixed solution, wherein the compound containing [CN4H7] is CN4H7Cl, CN4H8CO3, CN4H7NO3, or CN4H8SO4; the compound containing P is H3PO3 and K2HPO3; b. Ultrasonic treatment is performed on the mixed solution in step a to fully dissolve it to obtain a clear solution. The container is tightly sealed with a polyvinyl chloride film and placed in a static environment without shaking, pollution, or air convection. Several small holes are punched in the sealing film and the solution is allowed to stand at room temperature for 10-20 days. Subsequently, crystals in the solution precipitate and gradually grow, thereby obtaining hydroxyaminoguanidine phosphite nonlinear optical crystals.

3. Use of the hydroxyaminoguanidine phosphite nonlinear optical crystal as claimed in claim 1 in preparing harmonic light output of the 1064nm fundamental frequency light output by an Nd:YAG laser for frequency doubling, tripling, quadrupling and quintupleting.

4. Use of the hydroxyaminoguanidine phosphite nonlinear optical crystal as claimed in claim 1 in the preparation of ultraviolet frequency-doubled light output below 213 nm.

5. Use of the hydroxyaminoguanidine phosphite nonlinear optical crystal according to claim 1 in the preparation of a frequency doubling generator, an up- or down-frequency converter or an optical parametric oscillator.

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