Compound antimony phosphite, antimony phosphite nonlinear optical crystal and preparation method and application of antimony phosphite nonlinear optical crystal

Abstract

The invention provides a compound antimony phosphite, an antimony phosphite nonlinear optical crystal and a preparation method and application thereof, the chemical formula of the compound is SbH3P2O6, the molecular weight is 282.7, and the compound is prepared by adopting a vacuum packaging method or a room temperature solution method; the chemical formula of the compound of the crystal is SbH3P2O6, the molecular weight is 282.7, the compound belongs to a monoclinic system, the space group is Pc, the cell parameters are as follows: a = 7.6318 (12), b = 5.3723 (9), c = 7.5537 (12), alpha = 90 degrees, beta = 108.154 (6) degrees, gamma = 90 degrees, the unit cell volume is 294.29 (8) 3, the frequency-doubled effect of the crystal is about two times that of KH2PO4 (KDP), the ultraviolet cut-off edge is lower than 204 nm, the crystal is grown by adopting a hydrothermal method, a vacuum packaging method or a room temperature solution method, the chemical stability of the crystal is good, and the crystal is suitable for large-scale production. The short-wavelength nonlinear optical crystal can be applied to an all-solid-state laser as a short-wavelength nonlinear optical crystal.

Description

Technical Field

[0001] The invention relates to a compound antimony phosphite SbH3P2O6 and an antimony phosphite SbH3P2O6 nonlinear optical crystal as well as a preparation method and application thereof. Background Art

[0002] Due to its high energy and high beam quality, ultraviolet lasers have important applications in lithography, micromachining, optoelectronic devices and many other fields. Frequency conversion through nonlinear optical crystals is one of the most effective methods to output ultraviolet lasers. So far, the short-wavelength nonlinear optical crystals currently in practical use are β-BaB2O4, LiB3O5 and KBe2BO3F2 crystals invented by Chinese scientists, but due to the limitations of their crystal structure and some performance, they are still unable to be truly industrialized to meet the needs of scientific and technological development. Among them, the birefringence of β-BaB2O4 crystal is too large, the acceptance angle that meets the phase matching condition is small, and the walk-off angle is large, resulting in low frequency conversion efficiency and poor spot quality when realizing laser output; the birefringence of LiB3O5 crystal is too small, and the shortest phase matching wavelength is only 276nm, and it is impossible to output 266nm or shorter wavelength lasers through direct frequency doubling; KBe2BO3F2 crystal is restricted by intrinsic defects (weak interlayer forces in the structure), the layered growth habit of the crystal is very serious, and it is not easy to grow large-sized crystals. Therefore, it is of great significance and practical value to prepare and synthesize new short-wavelength nonlinear optical crystal materials with excellent comprehensive performance.

[0003] In previous studies, the present invention has three related patents: near-ultraviolet nonlinear optical crystal rubidium antimony fluoride selenate and its preparation method and application (patent application number CN202111191797.4), a preparation method of a near-ultraviolet nonlinear functional material and its application (patent application number CN202111192686.5), a bifunctional optical crystal rubidium antimony pyrophosphate with a Cairo pentagonal 2D layered structure and its preparation method and application (patent application number CN202111185475.9). The main difference between the present invention and the above three patents is that the compound SbH3P2O6 described in the present invention has a space group of Pc and belongs to the monoclinic system. In addition, the growth habits, key parameters of the growth process, and the linear and nonlinear optical properties of the crystal are all different from the previous six. Summary of the invention

[0004] The present invention aims to provide a compound antimony phosphite, the chemical formula of the compound is SbH3P2O6, the molecular weight is 282.7, and the compound is prepared by a vacuum packaging method or a room temperature solution method.

[0005] Another object of the present invention is to provide an antimony phosphite SbH3P2O6 nonlinear optical crystal, the chemical formula of the crystal is SbH3P2O6, the molecular weight is 282.7, it belongs to the monoclinic system, the space group is Pc, and the unit cell parameters are α=90°,β=108.154(6)°,γ=90°,the unit cell volume is

[0006] Another object of the present invention is to provide a method for preparing antimony phosphite SbH3P2O6 nonlinear optical crystals, using a hydrothermal method, a vacuum packaging method, or a room temperature solution method to grow the crystals.

[0007] Another object of the present invention is to provide the use of antimony phosphite SbH3P2O6 nonlinear optical crystal.

[0008] The antimony phosphite compound described in the invention has a chemical formula of SbH3P2O6 and a molecular weight of 282.7 and is prepared by a vacuum packaging method or a room temperature solution method.

[0009] The preparation method of the compound antimony phosphite adopts a vacuum packaging method or a room temperature solution method, and the specific operation is carried out according to the following steps:

[0010] The vacuum packaging method is used to prepare the compound antimony phosphite:

[0011] The Sb-containing compound and the P-containing compound were mixed evenly in a graphite crucible at a molar ratio of Sn:P=1:2, and then the graphite crucible was placed in a quartz tube, and the quartz tube was evacuated to a vacuum degree of 1×10 -3 Pa, sealed at high temperature, placed in a muffle furnace, heated to 200-250°C at a rate of 5-10°C / h, kept at a constant temperature for 24-120 hours, and then cooled to room temperature at a rate of 2°C / h to obtain compound SbH3P2O6, wherein the Sb-containing compound is Sb2O3, SbF3, SbCl3; the P-containing compound is H3PO3;

[0012] The room temperature solution method is used to prepare the compound antimony phosphite:

[0013] The Sb-containing compound and the P-containing compound are uniformly mixed at a molar ratio of Sn:P=1:2, put into a clean plastic container, add 20-100 mL of deionized water, and then ultrasonicate to fully mix and dissolve, filter with filter paper to obtain a mixed solution, and then seal with plastic wrap, poke a number of small holes in the seal, and stand at a temperature of 40-50°C for 5-20 days to obtain the compound SbH3P2O6, wherein the Sb-containing compound is Sb2O3, SbF3, SbCl3; the P-containing compound is H3PO3.

[0014] An antimony phosphite nonlinear optical crystal, the chemical formula of the crystal is SbH3P2O6, the molecular weight is 282.7, belongs to the monoclinic system, the space group is Pc, and the unit cell parameters are α=90°,β=108.154(6)°,γ=90°,the unit cell volume is

[0015] The method for preparing the antimony phosphite nonlinear optical crystal adopts a hydrothermal method, a vacuum packaging method or a room temperature solution method to grow the crystal;

[0016] The hydrothermal method for growing antimony phosphite nonlinear optical crystals is specifically performed in the following steps:

[0017] a. Mix the Sb-containing compound and the P-containing compound in a molar ratio of Sn:P=1:2, put them into the inner lining of a 23ml reactor, add deionized water as a solvent, place them in an oven, heat the temperature to 220°C at a rate of 20°C / h, keep the temperature constant for 24-120 hours, and then cool to room temperature at a cooling rate of 2°C / h to obtain SbH3P2O6 polycrystalline powder, wherein the Sb-containing compound is Sb2O3, SbF3, SbCl3; and the P-containing compound is H3PO3;

[0018] b. Dissolve the SbH3P2O6 polycrystalline powder obtained in step a in deionized water, then treat with ultrasonic waves to fully mix and dissolve it, and filter with filter paper to obtain a mixed solution;

[0019] c. Transfer the mixed solution obtained in step b into the liner of a clean, pollution-free autoclave with a volume of 100 mL, and tighten and seal the autoclave;

[0020] d. Place the autoclave in a constant temperature box, raise the temperature to 180-250°C, keep the temperature constant for 5-8 days, and then cool it down to room temperature at a rate of 5-25°C / day to obtain a SbH3P2O6 nonlinear optical crystal;

[0021] The vacuum packaging method for growing antimony phosphite nonlinear optical crystals is specifically performed in the following steps:

[0022] a. The Sb-containing compound and the P-containing compound are mixed uniformly in a molar ratio of Sn:P=1:2, and loaded into the inner lining of a 23 ml reactor, deionized water is added as a solvent, and the mixture is placed in an oven and heated to 220°C, and kept at a constant temperature for 24-120 hours to obtain SbH3P2O6 polycrystalline powder, wherein the Sb-containing compound is Sb2O3, SbF3, and SbCl3; and the P-containing compound is H3PO3;

[0023] b. The SbH3P2O6 polycrystalline powder obtained in step a is mixed evenly with the co-solvent in a molar ratio of 0-1:0.1-6, and the mixture is placed in a graphite crucible, and the graphite crucible is placed in a quartz tube, and the quartz tube is evacuated to a vacuum degree of 1×10 -3 Pa, sealed at high temperature and placed in a muffle furnace, heated to 200-250°C, kept constant temperature for 24-120 hours, and then cooled to room temperature at a rate of 0.1-3°C / h to obtain SbH3P2O6 nonlinear optical crystal, wherein the co-solvent is H3PO3;

[0024] The specific operation of growing antimony phosphite nonlinear optical crystal by room temperature solution method is carried out in the following steps:

[0025] a. The Sb-containing compound and the P-containing compound are mixed uniformly in a molar ratio of Sn:P=1:2, and loaded into the inner lining of a 23 ml reactor, deionized water is added as a solvent, and the mixture is placed in an oven and heated to 220°C, and kept at a constant temperature for 24-120 hours to obtain SbH3P2O6 polycrystalline powder, wherein the Sb-containing compound is Sb2O3, SbF3, and SbCl3; and the P-containing compound is H3PO3;

[0026] b. Place the SbH3P2O6 polycrystalline powder obtained in step a into a clean plastic container, add 20-100 mL of deionized water, and then perform ultrasonic treatment to fully mix and dissolve the powder, and filter the mixture with filter paper to obtain a mixed solution;

[0027] c. Place the mixed solution obtained in step b in a clean plastic container, seal it with weighing paper, place it in a static environment without shaking, pollution, or air convection, pierce several small holes in the seal to adjust the evaporation rate of water in the aqueous solution, and let it stand at 40-50° C. for 5-20 days;

[0028] d. Waiting for the solution in step c to grow crystal particles at the bottom of the container until the size of the crystal particles no longer changes significantly, thereby obtaining seed crystals;

[0029] e. Select the seed crystal with better quality in step d, suspend it in the mixed solution prepared in step b, and let it stand and grow at a temperature of 40-50° C. for 10-30 days to obtain SbH3P2O6 nonlinear optical crystal.

[0030] The antimony phosphite nonlinear optical crystal is used in preparing the 1064nm fundamental frequency light output by the Nd:YAG laser for double-frequency and triple-frequency harmonic light output.

[0031] The antimony phosphite nonlinear optical crystal is used in preparing a short-wavelength frequency-doubled light output of 355nm.

[0032] The antimony phosphite nonlinear optical crystal is used in preparing a frequency doubling generator, an up or down frequency converter or an optical parametric oscillator.

[0033] The preparation method of the antimony phosphite nonlinear optical crystal of the present invention comprises a quartz tube, a graphite crucible, a plastic cup, and a hydrothermal kettle lined with polytetrafluoroethylene or a stainless steel liner equipped with a platinum sleeve. When the container is a quartz tube, it needs to be evacuated before sealing to prevent the quartz tube from bursting due to volatilization of the raw materials during the reaction. When the container is a plastic cup, the container must be cleaned with acid first, then rinsed with deionized water, and dried.

[0034] In the method for preparing the antimony phosphite nonlinear optical crystal of the present invention, the resistance furnace used in the preparation process is a muffle furnace or a drying box.

[0035] By adopting the preparation method of antimony phosphite nonlinear optical crystal described in the present invention, SbH3P2O6 nonlinear optical crystal with a size of millimeter level is obtained by this method. By using a large-sized container and extending the growth period of the crystal, a corresponding large-sized nonlinear optical crystal SbH3P2O6 can be obtained. During the growth of the SbH3P2O6 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 to obtain large-sized crystals.

[0036] The large-sized SbH3P2O6 nonlinear optical crystal obtained by the preparation method of the antimony phosphite nonlinear optical crystal 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 SbH3P2O6 nonlinear optical crystal has the advantages of a light transmission band of about 204nm, stable physical and chemical properties, not easy to deliquesce, easy to process and store, etc. BRIEF DESCRIPTION OF THE DRAWINGS

[0037] Figure 1 The powder XRD spectrum of the compound SbH3P2O6 of the present invention;

[0038] Figure 2 It is a structural diagram of the SbH3P2O6 crystal of the present invention;

[0039] Figure 3 This is a working principle diagram of the nonlinear optical device made of SbH3P2O6 crystal of the present invention, wherein 1 is a laser, 2 is an emitted light beam, 3 is a SbH3P2O6 crystal, 4 is an output light beam, and 5 is a filter. DETAILED DESCRIPTION

[0040] The present invention is further described below in conjunction with the examples. It should be noted that the following examples cannot be used to limit the scope of protection of the present invention, and any improvements made on the basis of the present invention do not violate the spirit of the present invention. The raw materials or equipment used in the present invention, unless otherwise specified, are all commercially available.

[0041] Example 1

[0042] According to the reaction formula: Sb2O3+4H3PO3→2SbH3P2O6+3H2O, the compound SbH3P2O6 is synthesized by vacuum packaging method:

[0043] Sb2O3 and H3PO3 were mixed evenly in a molar ratio of 1:4 and loaded into a graphite crucible. The graphite crucible was then placed into a quartz tube of Φ40 mm. The quartz tube was evacuated to a vacuum degree of 1×10 -3 Pa, sealed at high temperature, placed in a muffle furnace, heated to 250°C at a rate of 5°C / h, kept at this temperature for 72 hours, and then cooled to room temperature at a rate of 2°C / h to obtain a polycrystalline powder of the compound SbH3P2O6.

[0044] Example 2

[0045] According to the reaction formula: Sb2O3+SbF3+6H3PO3→3SbH3P2O6+3HF+3H2O, the compound SbH3P2O6 is synthesized by vacuum packaging method:

[0046] Sb2O3, SbF3, and H3PO3 were mixed evenly in a molar ratio of 1:1:6 and loaded into a graphite crucible. The graphite crucible was then placed in a Φ40 mm quartz tube and the quartz tube was evacuated to a vacuum degree of 1×10 -3 Pa, sealed at high temperature, placed in a muffle furnace, heated to 200°C at a rate of 6°C / h, kept at this temperature for 24 hours, and then cooled to room temperature at a rate of 2°C / h to obtain a polycrystalline powder of the compound SbH3P2O6.

[0047] Example 3

[0048] According to the reaction formula: SbF3+2H3PO3→SbH3P2O6+3HF, the compound SbH3P2O6 was synthesized by vacuum packaging method:

[0049] SbF3 and H3PO3 were mixed evenly in a molar ratio of 1:2 and loaded into a graphite crucible. The graphite crucible was then placed into a quartz tube of Φ40 mm. The quartz tube was evacuated to a vacuum degree of 1×10 -3 Pa, sealed at high temperature, placed in a muffle furnace, heated to 220°C at a rate of 7°C / h, kept at this temperature for 36 hours, and then cooled to room temperature at a rate of 2°C / h to obtain polycrystalline powder of the compound SbH3P2O6.

[0050] Example 4

[0051] According to the reaction formula: Sb2O3+SbCl3+6H3PO3→3SbH3P2O6+3HCl+3H2O, the compound SbH3P2O6 was synthesized by vacuum packaging method:

[0052] Sb2O3, SbCl3, and H3PO3 were mixed evenly in a molar ratio of 1:1:6 and loaded into a graphite crucible. The graphite crucible was then placed in a Φ40 mm quartz tube and the quartz tube was evacuated to a vacuum degree of 1×10 -3 Pa, sealed at high temperature, placed in a muffle furnace, heated to 230°C at a rate of 8°C / h, kept at this temperature for 96 hours, and then cooled to room temperature at a rate of 2°C / h to obtain a polycrystalline powder of the compound SbH3P2O6.

[0053] Example 5

[0054] According to the reaction formula: SbCl3+2H3PO3→SbH3P2O6+3HCl, the compound SbH3P2O6 was synthesized by vacuum packaging method:

[0055] SbCl3 and H3PO3 were mixed evenly in a molar ratio of 1:2 and loaded into a graphite crucible. The graphite crucible was then placed into a Φ40 mm quartz tube and the quartz tube was evacuated to a vacuum degree of 1×10 -3 Pa, sealed at high temperature, placed in a muffle furnace, heated to 240°C at a rate of 10°C / h, kept at this temperature for 120 hours, and then cooled to room temperature at a rate of 2°C / h to obtain polycrystalline powder of the compound SbH3P2O6.

[0056] Example 6

[0057] According to the reaction formula: Sb2O3+4H3PO3→2SbH3P2O6+3H2O, the room temperature solution method was used to synthesize the compound SbH3P2O6: Sb2O3 and H3PO3 were evenly mixed in a molar ratio of 1:4, put into a clean plastic container, 20 mL of deionized water was added, and then ultrasonic treatment was performed to fully mix and dissolve, and the mixed solution was filtered with filter paper to obtain a mixed solution, and then sealed with plastic wrap, and a number of small holes were pierced in the seal, and the polycrystalline powder of the compound SbH3P2O6 was obtained by standing at a temperature of 50°C for 5 days.

[0058] Example 7

[0059] According to the reaction formula: Sb2O3+SbF3+6H3PO3→3SbH3P2O6+3HF+3H2O, the compound SbH3P2O6 was synthesized by room temperature solution method:

[0060] Sb2O3, SbF3, and H3PO3 were mixed evenly in a molar ratio of 1:1:6, placed in a clean plastic container, 50 mL of deionized water was added, and then ultrasonic treatment was performed to fully mix and dissolve, and a mixed solution was obtained by filtering with filter paper. The container was sealed with plastic wrap, and several small holes were punched in the seal, and the container was left to stand at 40°C for 10 days to obtain a polycrystalline powder of the compound SbH3P2O6.

[0061] Example 8

[0062] According to the reaction formula: SbF3+2H3PO3→SbH3P2O6+3HF, the room temperature solution method was used to synthesize the compound SbH3P2O6: SbF3 and H3PO3 were evenly mixed in a molar ratio of 1:2, put into a clean plastic container, added with 80 mL of deionized water, and then ultrasonically treated to fully mix and dissolve, filtered with filter paper to obtain a mixed solution, sealed with plastic wrap, pierced the seal with several small holes, and allowed to stand at 45°C for 15 days to obtain a polycrystalline powder of the compound SbH3P2O6.

[0063] Example 9

[0064] According to the reaction formula: Sb2O3+SbCl3+6H3PO3→3SbH3P2O6+3HCl+3H2O, the compound SbH3P2O6 was synthesized by room temperature solution method:

[0065] Sb2O3, SbCl3 and H3PO3 were mixed evenly in a molar ratio of 1:1:6, put into a clean plastic container, added with 100 mL of deionized water, and then ultrasonicated to fully mix and dissolve, filtered with filter paper to obtain a mixed solution, sealed with plastic wrap, pierced several small holes in the seal, and allowed to stand at 40°C for 20 days to obtain a polycrystalline powder of the compound SbH3P2O6.

[0066] Example 10

[0067] According to the reaction formula: SbCl3+2H3PO3→SbH3P2O6+3HCl, the room temperature solution method was used to synthesize the compound SbH3P2O6: SbCl3 and H3PO3 were evenly mixed in a molar ratio of 1:2, put into a clean plastic container, 70 mL of deionized water was added, and then ultrasonic treatment was performed to fully mix and dissolve, and the mixed solution was filtered with filter paper to obtain a mixed solution, and the seal was sealed with plastic wrap, and a number of small holes were pierced in the seal, and the polycrystalline powder of the compound SbH3P2O6 was obtained by standing at 40°C for 18 days.

[0068] Embodiment 11

[0069] According to the reaction formula: Sb2O3+4H3PO3→2SbH3P2O6+3H2O, the SbH3P2O6 nonlinear optical crystal is grown by hydrothermal method:

[0070] a. Evenly mix Sb2O3 and H3PO3 in a molar ratio of 1:4, load into the inner lining of a 23ml reactor, add 15mL of deionized water as solvent, seal the mouth of the reactor tightly, place it in an oven, heat it to 220℃ at a rate of 20℃ / h, keep the temperature constant for 24 hours, and then cool it to room temperature at a rate of 2℃ / h to obtain polycrystalline powder of SbH3P2O6.

[0071] b. Dissolve the SbH3P2O6 polycrystalline powder obtained in step a in deionized water, then treat with ultrasonic waves to fully mix and dissolve it, and filter with filter paper to obtain a mixed solution;

[0072] c. Transfer the mixed solution obtained in step b into the liner of a clean, pollution-free autoclave with a volume of 100 mL, and tighten and seal the autoclave;

[0073] d. Place the autoclave in a constant temperature box, raise the temperature to 180°C, keep the temperature constant for 5 days, and then cool it down to room temperature at a cooling rate of 5°C / day to obtain a SbH3P2O6 nonlinear optical crystal with a size of 4mm×3mm×1mm.

[0074] Example 12

[0075] According to the reaction formula: Sb2O3+SbF3+6H3PO3→3SbH3P2O6+3HF+3H2O, the SbH3P2O6 nonlinear optical crystal is grown by hydrothermal method:

[0076] a. Sb2O3, SbF3, and H3PO3 were mixed evenly in a molar ratio of 1:1:6, and loaded into the inner lining of a 23 ml reactor. 15 mL of deionized water was added as a solvent. The mouth of the reactor was tightly sealed and placed in an oven at a rate of 20°C / h to 220°C, kept at a constant temperature for 36 hours, and then cooled to room temperature at a rate of 2°C / h to obtain polycrystalline powder of SbH3P2O6;

[0077] b. Dissolve the SbH3P2O6 polycrystalline powder obtained in step a in deionized water, then treat with ultrasonic waves to fully mix and dissolve it, and filter with filter paper to obtain a mixed solution;

[0078] c. Transfer the mixed solution obtained in step b into the liner of a clean, pollution-free autoclave with a volume of 100 mL, and tighten and seal the autoclave;

[0079] d. Place the autoclave in a constant temperature box, raise the temperature to 200°C, keep the temperature constant for 6 days, and then cool it down to room temperature at a cooling rate of 15°C / day to obtain a SbH3P2O6 nonlinear optical crystal with a size of 3mm×2mm×1mm.

[0080] Example 13

[0081] According to the reaction formula: SbF3+2H3PO3→SbH3P2O6+3HF, the SbH3P2O6 nonlinear optical crystal is grown by hydrothermal method:

[0082] a. Mix SbF3 and H3PO3 in a molar ratio of 1:2, load into the inner lining of a 100 ml reactor, add 15 mL of deionized water as a solvent, seal the mouth of the reactor tightly, place it in an oven, heat it to 220°C at a rate of 20°C / h, keep it at a constant temperature for 72 hours, and then cool it down to room temperature at a rate of 2°C / h to obtain polycrystalline powder of SbH3P2O6.

[0083] b. Dissolve the SbH3P2O6 polycrystalline powder obtained in step a in deionized water, then treat with ultrasonic waves to fully mix and dissolve it, and filter with filter paper to obtain a mixed solution;

[0084] c. Transfer the mixed solution obtained in step b into the liner of a clean, pollution-free autoclave with a volume of 100 mL, and tighten and seal the autoclave;

[0085] d. Place the high-pressure reactor in a constant temperature box, raise the temperature to 200°C, keep the temperature constant for 6 days, and then cool it down to room temperature at a cooling rate of 10°C / day to obtain a SbH3P2O6 nonlinear optical crystal with a size of 4mm×2mm×2mm.

[0086] Embodiment 14

[0087] According to the reaction formula: Sb2O3+SbCl3+6H3PO3→3SbH3P2O6+3HCl+3H2O, the SbH3P2O6 nonlinear optical crystal is grown by hydrothermal method:

[0088] a. Sb2O3, SbCl3, and H3PO3 were mixed evenly in a molar ratio of 1:1:6, and loaded into the inner lining of a 23 ml reactor. 15 mL of deionized water was added as a solvent. The mouth of the reactor was tightly sealed and placed in an oven at a rate of 20°C / h to 220°C, kept at a constant temperature for 120 hours, and then cooled to room temperature at a rate of 2°C / h to obtain polycrystalline powder of SbH3P2O6;

[0089] b. Dissolve the SbH3P2O6 polycrystalline powder obtained in step a in deionized water, then treat with ultrasonic waves to fully mix and dissolve it, and filter with filter paper to obtain a mixed solution;

[0090] c. Transfer the mixed solution obtained in step b into the liner of a clean, pollution-free autoclave with a volume of 100 mL, and tighten and seal the autoclave;

[0091] d. Place the autoclave in a constant temperature box, raise the temperature to 210°C, keep the temperature constant for 7 days, and then cool it down to room temperature at a cooling rate of 18°C / day to obtain a SbH3P2O6 nonlinear optical crystal with a size of 5mm×3mm×1mm.

[0092] Embodiment 15

[0093] According to the reaction formula: SbCl3+2H3PO3→SbH3P2O6+3HCl, the SbH3P2O6 nonlinear optical crystal is grown by hydrothermal method:

[0094] a. SbCl3 and H3PO3 were mixed evenly at a molar ratio of 1:2, and loaded into the inner lining of a 23 ml reactor. 15 mL of deionized water was added as a solvent. The mouth of the reactor was tightly sealed and placed in an oven at a rate of 20°C / h to 220°C, kept at a constant temperature for 72 hours, and then cooled to room temperature at a rate of 2°C / h to obtain polycrystalline powder of SbH3P2O6;

[0095] b. Dissolve the SbH3P2O6 polycrystalline powder obtained in step a in deionized water, then treat with ultrasonic waves to fully mix and dissolve it, and filter with filter paper to obtain a mixed solution;

[0096] c. Transfer the mixed solution obtained in step b into the liner of a clean, pollution-free autoclave with a volume of 100 mL, and tighten and seal the autoclave;

[0097] d. Place the autoclave in a constant temperature box, raise the temperature to 250°C, keep the temperature constant for 8 days, and then cool it down to room temperature at a cooling rate of 25°C / day to obtain a SbH3P2O6 nonlinear optical crystal with a size of 4mm×4mm×2mm.

[0098] Example 16

[0099] Growing SbH3P2O6 nonlinear optical crystals using vacuum packaging method:

[0100] The SbH3P2O6 polycrystalline powder obtained in Example 1 was mixed with the co-solvent H3PO3 in a molar ratio of 1:0.1 and uniformly loaded into a graphite crucible. The graphite crucible was then placed in a quartz tube of Φ40 mm. The quartz tube was evacuated to a vacuum degree of 1×10 -3 Pa, sealed at high temperature, placed in a muffle furnace, heated to 220°C, kept constant for 72 hours, and then cooled to room temperature at a cooling rate of 1°C / h to obtain a SbH3P2O6 nonlinear optical crystal with a size of 2mm×2mm×1mm.

[0101] Embodiment 17

[0102] Growing SbH3P2O6 nonlinear optical crystals using vacuum packaging method:

[0103] The SbH3P2O6 polycrystalline powder obtained in Example 2 was mixed evenly with the co-solvent H3PO3 at a molar ratio of 1:0.5, and then placed in a graphite crucible. The graphite crucible was then placed in a quartz tube of Φ40 mm, and the quartz tube was evacuated to a vacuum degree of 1×10 - 3 Pa, sealed at high temperature, placed in a muffle furnace, heated to 200 ° C, kept constant temperature for 120 hours, and then cooled to room temperature at a rate of 0.1 ° C / h to obtain a 4mm × 3mm × 2mm SbH3P2O6 nonlinear optical crystal.

[0104] Embodiment 18

[0105] Growing SbH3P2O6 nonlinear optical crystals using vacuum packaging method:

[0106] The SbH3P2O6 polycrystalline powder obtained in Example 3 was mixed evenly with the co-solvent H3PO3 in a molar ratio of 1:1, and then placed in a graphite crucible. The graphite crucible was then placed in a quartz tube of Φ40 mm, and the quartz tube was evacuated to a vacuum degree of 1×10 -3 Pa, sealed at high temperature, placed in a muffle furnace, heated to 210°C, kept constant for 24 hours, and then cooled to room temperature at a rate of 1°C / h to obtain a SbH3P2O6 nonlinear optical crystal.

[0107] Embodiment 19

[0108] Growing SbH3P2O6 nonlinear optical crystals using vacuum packaging method:

[0109] The SbH3P2O6 polycrystalline powder obtained in Example 4 was mixed evenly with the co-solvent H3PO3 in a molar ratio of 1:4, and then placed in a graphite crucible. The graphite crucible was then placed in a quartz tube of Φ40 mm, and the quartz tube was evacuated to a vacuum degree of 1×10 -3 Pa, sealed at high temperature, placed in a muffle furnace, heated to 230 ° C, kept constant temperature for 80 hours, and then cooled to room temperature at a rate of 2 ° C / h to obtain a 3mm × 3mm × 2mm SbH3P2O6 nonlinear optical crystal.

[0110] Embodiment 20

[0111] Growing SbH3P2O6 nonlinear optical crystals using vacuum packaging method:

[0112] The SbH3P2O6 polycrystalline powder obtained in Example 5 was mixed evenly with the co-solvent H3PO3 in a molar ratio of 1:6, and then placed in a graphite crucible. The graphite crucible was then placed in a quartz tube of Φ40 mm, and the quartz tube was evacuated to a vacuum degree of 1×10 -3Pa, sealed at high temperature, placed in a muffle furnace, heated to 250°C, kept constant for 100 hours, and then cooled to room temperature at a rate of 3°C / h to obtain a 3mm×2mm×1mm SbH3P2O6 nonlinear optical crystal.

[0113] Embodiment 21

[0114] SbH3P2O6 nonlinear optical crystals were grown using room temperature solution method:

[0115] The compound SbH3P2O6 polycrystalline powder obtained in Example 6 was placed in a clean plastic container, 100 mL of deionized water was added, and then ultrasonic treatment was performed to fully mix and dissolve, and a mixed solution was obtained by filtering with filter paper;

[0116] The obtained mixed solution is placed in a clean plastic container, sealed with weighing paper, placed in a static environment without shaking, pollution, and air convection, and several small holes are punched in the seal to adjust the evaporation rate of water in the aqueous solution, and left to stand at 40°C for 20 days;

[0117] Waiting for the solution to grow crystal particles at the bottom of the container until the size of the crystal particles no longer changes significantly, a seed crystal is obtained;

[0118] A seed crystal with better quality was selected, suspended in the prepared mixed solution, and allowed to stand for growth at 40°C for 30 days to obtain a SbH3P2O6 nonlinear optical crystal with a size of 8mm×8mm×6mm.

[0119] Embodiment 22

[0120] SbH3P2O6 nonlinear optical crystals were grown using room temperature solution method:

[0121] The SbH3P2O6 polycrystalline powder obtained in Example 7 was placed in a clean plastic container, 20 mL of deionized water was added, and then ultrasonic treatment was performed to fully mix and dissolve the powder, and the powder was filtered with filter paper to obtain a mixed solution;

[0122] The obtained mixed solution is placed in a clean plastic container, sealed with weighing paper, placed in a static environment without shaking, pollution, and air convection, and several small holes are punched in the seal to adjust the evaporation rate of water in the aqueous solution, and left to stand at 45°C for 10 days;

[0123] Waiting for the solution to grow crystal particles at the bottom of the container until the size of the crystal particles no longer changes significantly, a seed crystal is obtained;

[0124] A seed crystal with better quality was selected, suspended in the prepared mixed solution, and allowed to stand for growth at 45° C. for 10 days to obtain a SbH 3 P 2 O 6 nonlinear optical crystal with a size of 8 mm×7 mm×3 mm.

[0125] Embodiment 23

[0126] SbH3P2O6 nonlinear optical crystals were grown using room temperature solution method:

[0127] The SbH3P2O6 polycrystalline powder obtained in Example 8 was placed in a clean plastic container, 50 mL of deionized water was added, and then ultrasonic treatment was performed to fully mix and dissolve the powder, and the powder was filtered with filter paper to obtain a mixed solution;

[0128] The obtained mixed solution is placed in a clean plastic container, sealed with weighing paper, placed in a static environment without shaking, pollution, and air convection, and several small holes are punched in the seal to adjust the evaporation rate of water in the aqueous solution, and left to stand at 48°C for 12 days;

[0129] Waiting for the solution to grow crystal particles at the bottom of the container until the size of the crystal particles no longer changes significantly, a seed crystal is obtained;

[0130] A seed crystal with better quality was selected, suspended in the prepared mixed solution, and allowed to stand for growth at 42° C. for 20 days, thereby obtaining a SbH 3 P 2 O 6 nonlinear optical crystal with a size of 9 mm×6 mm×2 mm.

[0131] Embodiment 24

[0132] SbH3P2O6 nonlinear optical crystals were grown using room temperature solution method:

[0133] The SbH3P2O6 polycrystalline powder obtained in Example 9 was placed in a clean plastic container, 80 mL of deionized water was added, and then ultrasonic treatment was performed to fully mix and dissolve the powder, and the powder was filtered with filter paper to obtain a mixed solution;

[0134] The obtained mixed solution is placed in a clean plastic container, sealed with weighing paper, placed in a static environment without shaking, pollution, and air convection, and several small holes are punched in the seal to adjust the evaporation rate of water in the aqueous solution, and left to stand at 50°C for 5 days;

[0135] Waiting for the solution to grow crystal particles at the bottom of the container until the size of the crystal particles no longer changes significantly, a seed crystal is obtained;

[0136] Select a seed crystal with good quality, suspend it in the mixed solution prepared in step b, and let it stand and grow for 30 days at a temperature of 50°C to obtain a SbH3P2O6 nonlinear optical crystal with a size of 9mm×7mm×6mm.

[0137] Embodiment 25

[0138] SbH3P2O6 nonlinear optical crystals were grown using room temperature solution method:

[0139] The SbH3P2O6 polycrystalline powder obtained in Example 10 was placed in a clean plastic container, 40 mL of deionized water was added, and then ultrasonic treatment was performed to fully mix and dissolve the powder, and the powder was filtered with filter paper to obtain a mixed solution;

[0140] The obtained mixed solution is placed in a clean plastic container, sealed with weighing paper, placed in a static environment without shaking, pollution, and air convection, and several small holes are punched in the seal to adjust the evaporation rate of water in the aqueous solution, and left to stand at 45°C for 12 days;

[0141] Waiting for the solution to grow crystal particles at the bottom of the container until the size of the crystal particles no longer changes significantly, a seed crystal is obtained;

[0142] A seed crystal with better quality was selected, suspended in the prepared mixed solution, and allowed to stand for growth at 45° C. for 20 days to obtain a SbH 3 P 2 O 6 nonlinear optical crystal with a size of 6 mm×5 mm×5 mm.

[0143] Embodiment 26

[0144] Any SbH3P2O6 crystal obtained in Examples 11-25 is processed in a matching direction, and the attached 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. The incident wavelength is 1064nm. The infrared light beam 2 with a wavelength of 1064nm emitted by the Q-switched Nd:YAG laser 1 is incident on the SbH3P2O6 single crystal 3, generating green doubled frequency light with a wavelength of 532nm. The output intensity is about twice that of KDP under the same conditions.

Claims

1. A compound antimony phosphite, characterized in that The compound has the chemical formula of SbH3P2O6 and a molecular weight of 282.7 and is prepared by a vacuum encapsulation method or a room temperature solution method.

2. The method for preparing the compound antimony phosphite according to claim 1, characterized in that The vacuum packaging method or room temperature solution method is used for preparation. The specific operation is carried out according to the following steps: The vacuum packaging method is used to prepare the compound antimony phosphite: The Sb-containing compound and the P-containing compound were mixed evenly in a graphite crucible at a molar ratio of Sn:P=1:2, and then the graphite crucible was placed in a quartz tube, and the quartz tube was evacuated to a vacuum degree of 1×10 −3 Pa, sealed at high temperature and placed in a muffle furnace, heated to 200-250 °C at a rate of 5-10 °C / h, kept at constant temperature for 24-120 hours, and then cooled to room temperature at a rate of 2 °C / h to obtain compound SbH3P2O6, wherein the Sb-containing compound is Sb2O3, SbF3, SbCl3; the P-containing compound is H3PO3; The room temperature solution method is used to prepare the compound antimony phosphite: The Sb-containing compound and the P-containing compound are mixed uniformly at a molar ratio of Sn:P=1:2, put into a clean plastic container, add 20-100 mL of deionized water, and then ultrasonicate to fully mix and dissolve, filter with filter paper to obtain a mixed solution, and then seal with plastic wrap, poke a number of small holes in the seal, and stand at a temperature of 40-50 ° C for 5-20 days to obtain the compound SbH3P2O6, wherein the Sb-containing compound is Sb2O3, SbF3, SbCl3; the P-containing compound is H3PO3.

3. An antimony phosphite nonlinear optical crystal, characterized in that The chemical formula of the crystal is SbH3P2O6, the molecular weight is 282.7, it belongs to the monoclinic system, and the space group is Pc , the unit cell parameters are a = 7.6318(12) Å, b = 5.3723(9) Å, c =7.5537(12) Å, α = 90°, β = 108.154(6)°, γ = 90°, the unit cell volume is 294.29(8) Å 3 .

4. The method for preparing the antimony phosphite nonlinear optical crystal according to claim 3, characterized in that Crystals are grown using hydrothermal, vacuum encapsulation or room temperature solution methods; The hydrothermal method for growing antimony phosphite nonlinear optical crystals is specifically performed in the following steps: a. The Sb-containing compound and the P-containing compound are mixed uniformly in a molar ratio of Sn:P=1:2, and the mixture is loaded into the inner lining of a 23 ml reactor, and deionized water is added as a solvent. The mixture is placed in an oven and heated to 220°C at a rate of 20°C / h, and kept at a constant temperature for 24-120 hours, and then cooled to room temperature at a cooling rate of 2°C / h to obtain SbH3P2O6 polycrystalline powder, wherein the Sb-containing compound is Sb2O3, SbF3, and SbCl3; and the P-containing compound is H3PO3; b. Dissolve the SbH3P2O6 polycrystalline powder obtained in step a in deionized water, then treat with ultrasonic waves to fully mix and dissolve it, and filter with filter paper to obtain a mixed solution; c. Transfer the mixed solution obtained in step b into the liner of a clean, pollution-free high-pressure reactor with a volume of 100 mL, and tighten and seal the reactor; d. Place the autoclave in a constant temperature box, raise the temperature to 180-250 °C, keep the temperature constant for 5-8 days, and then cool it down to room temperature at a rate of 5-25 °C / day to obtain a SbH3P2O6 nonlinear optical crystal; The vacuum packaging method for growing antimony phosphite nonlinear optical crystals is specifically performed in the following steps: a. Mix the Sb-containing compound and the P-containing compound in a molar ratio of Sn:P=1:2, put them into the lining of a 23 ml reactor, add deionized water as a solvent, place them in an oven and heat them to 220°C, and keep the temperature constant for 24-120 hours to obtain SbH3P2O6 polycrystalline powder, wherein the Sb-containing compound is Sb2O3, SbF3, SbCl3; and the P-containing compound is H3PO3; b. The SbH3P2O6 polycrystalline powder obtained in step a is mixed evenly with the co-solvent in a molar ratio of 0-1:0.1-6, and the mixture is placed in a graphite crucible, and the graphite crucible is placed in a quartz tube, and the quartz tube is evacuated to a vacuum degree of 1×10 −3 Pa, sealed at high temperature and placed in a muffle furnace, heated to 200-250 °C, kept constant temperature for 24-120 hours, and then cooled to room temperature at a rate of 0.1-3 °C / h to obtain SbH3P2O6 nonlinear optical crystal, wherein the co-solvent is H3PO3; The specific operation of growing antimony phosphite nonlinear optical crystal by room temperature solution method is carried out in the following steps: a. Mix the Sb-containing compound and the P-containing compound in a molar ratio of Sn:P=1:2, put them into the lining of a 23 ml reactor, add deionized water as a solvent, place them in an oven and heat them to 220°C, and keep the temperature constant for 24-120 hours to obtain SbH3P2O6 polycrystalline powder, wherein the Sb-containing compound is Sb2O3, SbF3, SbCl3; and the P-containing compound is H3PO3; b. Place the SbH3P2O6 polycrystalline powder obtained in step a into a clean plastic container, add 20-100 mL of deionized water, and then perform ultrasonic treatment to fully mix and dissolve the powder, and filter the mixture with filter paper to obtain a mixed solution; c. Place the mixed solution obtained in step b in a clean plastic container, seal it with weighing paper, place it in a static environment without shaking, pollution, or air convection, pierce several small holes in the seal to adjust the evaporation rate of water in the aqueous solution, and place it at 40-50° C. for 5-20 days; d. Waiting for the solution in step c to grow crystal particles at the bottom of the container until the size of the crystal particles no longer changes significantly, thereby obtaining seed crystals; e. Select the seed crystal with better quality in step d, suspend it in the mixed solution prepared in step b, and let it stand and grow at a temperature of 40-50° C. for 10-30 days to obtain SbH3P2O6 nonlinear optical crystal.

5. A use of the antimony phosphite nonlinear optical crystal as claimed in claim 3 in preparing the 1064 nm fundamental frequency light output by a Nd: YAG laser for double- and triple-harmonic light output.

6. Use of the antimony phosphite nonlinear optical crystal as claimed in claim 3 in the preparation of a short-wavelength frequency-doubled light output of 355 nm.

7. Use of the antimony phosphite nonlinear optical crystal as claimed in claim 3 in preparing a frequency doubling generator, an up or down frequency converter or an optical parametric oscillator.

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