Compounds antimony phosphite and antimony phosphite nonlinear optical crystals and methods of preparation and use

Abstract

The application provides a compound antimony subphosphate and a nonlinear optical crystal of antimony subphosphate, a preparation method and an application, 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; the chemical formula of the compound of the crystal is SbH3P2O6, the molecular weight is 282.7, the crystal belongs to a monoclinic system, the space group is Pc , the 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°, and the unit cell volume is 294.29 (8) Å 3 The frequency doubling effect of the crystal is about 2 times of that of KH2PO4 (KDP), the ultraviolet cutoff edge is lower than 204 nm, the crystal is grown by a hydrothermal method, a vacuum packaging method or a room temperature solution method, the chemical stability of the crystal is good, and the crystal can be applied to a short-wavelength nonlinear optical crystal in a full solid-state laser.

Description

TECHNICAL FIELD

[0001] The present application relates to a compound antimony subphosphate SbH3P2O6 and antimony subphosphate SbH3P2O6 nonlinear optical crystal and preparation method and use. BACKGROUND

[0002] Due to the high energy and high beam quality of ultraviolet laser, it has important application in photoetching, microprocessing, photoelectric device and many other fields. Frequency conversion through nonlinear optical crystal is one of the most effective methods to output ultraviolet laser. So far, the short-wavelength nonlinear optical crystals that have been practically used are β-BaB2O4, LiB3O5 and KBe2BO3F2 crystals invented by Chinese scientists, but due to the limitations of crystal structure and some properties, they still cannot be truly industrialized to meet the needs of 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 doubling conversion efficiency and poor spot quality when laser output is achieved; the birefringence of LiB3O5 crystal is too small, and the shortest phase matching wavelength is only 276 nm, which cannot output 266 nm or shorter wavelength laser through direct frequency doubling; the KBe2BO3F2 crystal is restricted by intrinsic defects (weak interlayer interaction in the structure), and the layered growth habit of the crystal is very serious, making it difficult to grow large-size 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 the previous research, there are three related patents: a near-ultraviolet nonlinear optical crystal fluorinated rubidium selenate antimony 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), and a bifunctional optical crystal rubidium antimony pyrophosphate with Cairo pentagonal 2D layered structure and its preparation method and application (patent application number CN202111185475.9). The main difference between the present application and the above three patents is that the compound SbH3P2O6 described in the present application has a space group of Pc and belongs to a monoclinic system. In addition, the growth habit, key parameters of the growth process, linear and nonlinear optical properties of the crystal are different from the previous six. SUMMARY

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

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

[0006] Another object of the present application is to provide antimony phosphite SbH3P2O6 nonlinear optical crystal, the chemical formula of the crystal is SbH3P2O6, the molecular weight is 282.7. It belongs to monoclinic system, the space group is Pc, the cell parameter is

[0007] Another object of the present application is to provide antimony phosphite SbH3P2O6 nonlinear optical crystal, the chemical formula of the crystal is SbH3P2O6, the molecular weight is 282.7. It belongs to monoclinic system, the space group is Pc, the cell parameter is

[0008] The compound antimony phosphite of the present application, the chemical formula of the compound is SbH3P2O6, the molecular weight is 282.7, and is prepared by vacuum packaging method or room temperature solution method.

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

[0010] The vacuum packaging method for preparing the compound antimony phosphite is as follows:

[0011] The Sb-containing compound and the P-containing compound are mixed uniformly according to the molar ratio Sb:P=1:2, and then are loaded into a graphite crucible, and then the graphite crucible is placed in a quartz tube, and the quartz tube is vacuumized, and the vacuum degree reaches 1x10 -3 Pa, and after high-temperature sealing, is placed in a muffle furnace, and is heated to 200-250 DEG C at a rate of 5-10 DEG C / h, and is kept at constant temperature for 24-120 hours, and then is cooled to room temperature at a rate of 2 DEG C / h, to obtain the compound SbH3P2O6, wherein the Sb-containing compound is Sb2O3, SbF3 or SbCl3, and the P-containing compound is H3PO3.

[0012] The room temperature solution method for preparing the compound antimony phosphite is as follows:

[0013] The Sb-containing compound and the P-containing compound are mixed uniformly according to the molar ratio Sb:P=1:2, and then are loaded into a graphite crucible, and then the graphite crucible is placed in a quartz tube, and the quartz tube is vacuumized, and the vacuum degree reaches 1x10 -3 Pa, and after high-temperature sealing, is placed in a muffle furnace, and is heated to 200-250 DEG C at a rate of 5-10 DEG C / h, and is kept at constant temperature for 24-120 hours, and then is cooled to room temperature at a rate of 2 DEG C / h, to obtain the compound SbH3P2O6, wherein the Sb-containing compound is Sb2O3, SbF3 or SbCl3, and the P-containing compound is H3PO3.

[0014] A antimony phosphite nonlinear optical crystal, the chemical formula of which is SbH3P2O6, the molecular weight of which is 282.7, which belongs to monoclinic system, the space group of which is Pc, and the cell parameter of which is

[0015] α=90°, β=108.154(6)°, γ=90°, and the unit cell volume is

[0016] A preparation method of the antimony phosphite nonlinear optical crystal, which adopts a hydrothermal method, a vacuum packaging method or a room temperature solution method to grow the crystal;

[0017] The hydrothermal method for growing the antimony phosphite nonlinear optical crystal is specifically operated according to the following steps:

[0018] a. A Sb-containing compound and a P-containing compound are uniformly mixed according to a molar ratio of Sb:P=1:2, and are loaded into an inner liner of a 23-ml reaction kettle, deionized water is added as a solvent, and the reaction kettle is placed in an oven and heated to 220°C at a rate of 20°C / h, and then is kept at the temperature for 24-120 hours, and then is cooled to room temperature at a rate of 2°C / h, so that SbH3P2O6 polycrystal powder is obtained, the Sb-containing compound is Sb2O3, SbF3 or SbCl3, and the P-containing compound is H3PO3;

[0019] b. The SbH3P2O6 polycrystal powder obtained in step a is dissolved in deionized water, and then is ultrasonically treated to be fully mixed and dissolved, and then is filtered by filter paper to obtain a mixed solution;

[0020] c. The mixed solution obtained in step b is transferred into a clean and uncontaminated inner liner of a 100-ml high-pressure reaction kettle, and the reaction kettle is tightly sealed;

[0021] d. The high-pressure reaction kettle is placed in a thermostat, and is heated to 180-250°C, and then is kept at the temperature for 5-8 days, and then is cooled to room temperature at a rate of 5-25°C / day, so that the SbH3P2O6 nonlinear optical crystal is obtained;

[0022] The vacuum packaging method for growing the antimony phosphite nonlinear optical crystal is specifically operated according to the following steps:

[0023] a. A Sb-containing compound and a P-containing compound are uniformly mixed according to a molar ratio of Sb:P=1:2, and are loaded into an inner liner of a 23-ml reaction kettle, deionized water is added as a solvent, and the reaction kettle is placed in an oven and heated to 220°C, and then is kept at the temperature for 24-120 hours, so that SbH3P2O6 polycrystal powder is obtained, the Sb-containing compound is Sb2O3, SbF3 or SbCl3, and the P-containing compound is H3PO3;

[0024] b. The SbH3P2O6 polycrystal powder obtained in step a is mixed with a cosolvent at a molar ratio of 0-1:0.1-6, and is loaded into a graphite crucible, which is then placed in a quartz tube. The quartz tube is vacuumized to a vacuum degree of 1x10 -3 Pa, and is placed in a muffle furnace after high-temperature sealing, and is heated to 200-250°C, and is kept at a constant temperature for 24-120 hours, and then is decreased to room temperature at a rate of 0.1-3°C / h, to obtain the SbH3P2O6 nonlinear optical crystal, wherein the cosolvent is H3PO3;

[0025] The specific operation of the room-temperature solution method for growing the antimony phosphite nonlinear optical crystal is performed according to the following steps:

[0026] a. A Sb-containing compound and a P-containing compound are mixed at a molar ratio of Sb:P=1:2, and are loaded into an inner liner of a 23-ml reaction kettle, and deionized water is added as a solvent, and is placed in an oven and heated to 220°C, and is kept at a constant temperature for 24-120 hours, to obtain SbH3P2O6 polycrystal powder, wherein the Sb-containing compound is Sb2O3, SbF3 or SbCl3, and the P-containing compound is H3PO3;

[0027] b. The SbH3P2O6 polycrystal powder obtained in step a is placed in a clean plastic container, 20-100 mL of deionized water is added, and then is treated by ultrasonic waves to make it fully mixed and dissolved, and is filtered by filter paper to obtain a mixed solution;

[0028] c. The mixed solution obtained in step b is placed in a clean plastic container, is sealed with weighing paper, and is placed in a static environment without shaking, pollution or air convection, a plurality of small holes are made on the sealing to adjust the evaporation rate of water in the aqueous solution, and is placed at 40-50°C for 5-20 days;

[0029] d. The solution in step c is allowed to grow crystal particles on the bottom of the container, until the size of the crystal particles no longer changes obviously, to obtain a seed crystal;

[0030] e. A seed crystal with good quality in step d is selected, and is hung in the mixed solution prepared in step b, and is placed at a temperature of 40-50°C for 10-30 days, to obtain the SbH3P2O6 nonlinear optical crystal.

[0031] The SbH3P2O6 nonlinear optical crystal is used in the preparation of a 1064nm fundamental frequency light output by an Nd:YAG laser, and is used in the 2-fold frequency and 3-fold frequency harmonic light output.

[0032] The SbH3P2O6 nonlinear optical crystal is used in the preparation of a 355nm short-wavelength frequency-doubled light output.

[0033] The application relates to a use of the antimony hypophosphite nonlinear optical crystal in preparation of a frequency doubling generator, an up or down frequency converter or an optical parametric oscillator.

[0034] The preparation method of the antimony hypophosphite nonlinear optical crystal is characterized by using a quartz tube, a graphite crucible, a plastic cup, a hydrothermal kettle with a polytetrafluoroethylene lining or a stainless steel lining provided with a platinum gold sleeve as the container in the preparation process.

[0035] The preparation method of the antimony hypophosphite nonlinear optical crystal is characterized by using a muffle furnace or a drying box as the electric resistance furnace in the preparation process.

[0036] The preparation method of the antimony hypophosphite nonlinear optical crystal is characterized by using a muffle furnace or a drying box as the electric resistance furnace in the preparation process.

[0037] The preparation method of the antimony hypophosphite nonlinear optical crystal is characterized by using a muffle furnace or a drying box as the electric resistance furnace in the preparation process. BRIEF DESCRIPTION OF DRAWINGS

[0038] Figure 1 The figure is a powder XRD spectrum of the compound SbH3P2O6 in the application;

[0039] Figure 2 The figure is a structure diagram of the SbH3P2O6 crystal in the application;

[0040] Figure 3 The figure is a working principle diagram of the nonlinear optical device made of the SbH3P2O6 crystal in the application, wherein 1 is a laser, 2 is an emitted light beam, 3 is the SbH3P2O6 crystal, 4 is an emitted light beam, 5 is a filter. DETAILED DESCRIPTION

[0041] The application will be further described in conjunction with the following examples. It should be noted that the following examples cannot be used as a limitation to the scope of the present application, and any improvement made on the basis of the present application will not deviate from the spirit of the present application. The raw materials or equipment used in the present application are commercially available, unless otherwise specified.

[0042] Example 1

[0043] The compound SbH3P2O6 is synthesized by vacuum sealing method according to the reaction formula: Sb2O3+4H3PO3→2SbH3P2O6+3H2O:

[0044] Sb2O3 and H3PO3 are mixed uniformly in a graphite crucible according to a molar ratio of 1:4, and then the graphite crucible is placed in a Φ40mm quartz tube. The quartz tube is vacuumed to a vacuum degree of 1x10 -3 Pa, and then placed in a muffle furnace after high-temperature sealing. The temperature is raised to 250°C at a rate of 5°C / h, and then kept constant for 72 hours. The temperature is then lowered to room temperature at a rate of 2°C / h, and the polycrystalline powder of the compound SbH3P2O6 is obtained.

[0045] Example 2

[0046] The compound SbH3P2O6 is synthesized by vacuum sealing method according to the reaction formula: Sb2O3+SbF3+6H3PO3→3SbH3P2O6+3HF+3H2O:

[0047] Sb2O3, SbF3 and H3PO3 are mixed uniformly in a graphite crucible according to a molar ratio of 1:1:6, and then the graphite crucible is placed in a Φ40mm quartz tube. The quartz tube is vacuumed to a vacuum degree of 1x10 -3 Pa, and then placed in a muffle furnace after high-temperature sealing. The temperature is raised to 200°C at a rate of 6°C / h, and then kept constant for 24 hours. The temperature is then lowered to room temperature at a rate of 2°C / h, and the polycrystalline powder of the compound SbH3P2O6 is obtained.

[0048] Example 3

[0049] The compound SbH3P2O6 is synthesized by vacuum sealing method according to the reaction formula: SbF3+2H3PO3→SbH3P2O6+3HF:

[0050] SbF3 and H3PO3 are mixed uniformly in a graphite crucible according to a molar ratio of 1:2, and then the graphite crucible is placed in a Φ40mm quartz tube. The quartz tube is vacuumed to a vacuum degree of 1x10 -3 Pa, and then placed in a muffle furnace after high-temperature sealing. The temperature is raised to 220°C at a rate of 7°C / h, and then kept constant for 36 hours. The temperature is then lowered to room temperature at a rate of 2°C / h, and the polycrystalline powder of the compound SbH3P2O6 is obtained.

[0051] Example 4

[0052] The compound SbH3P2O6was synthesized by vacuum sealing method according to the reaction formula: Sb2O3+SbCl3+6H3PO3→3SbH3P2O6+3HCl+3H2O:

[0053] Sb2O3, SbCl3, H3PO3 were mixed uniformly in a graphite crucible according to the molar ratio of 1:1:6, and then the graphite crucible was put into a Φ40mm quartz tube. The quartz tube was vacuumized, and the vacuum degree reached 1x10 -3 Pa. After high-temperature sealing, it was placed in a muffle furnace, and the temperature was raised to 230°C at a rate of 8°C / h. After constant temperature for 96 hours, it was cooled to room temperature at a rate of 2°C / h. Thus, the polycrystalline powder of the compound SbH3P2O6was obtained.

[0054] Example 5

[0055] The compound SbH3P2O6was synthesized by vacuum sealing method according to the reaction formula: SbCl3+2H3PO3→SbH3P2O6+3HCl:

[0056] SbCl3, H3PO3 were mixed uniformly in a graphite crucible according to the molar ratio of 1:2, and then the graphite crucible was put into a Φ40mm quartz tube. The quartz tube was vacuumized, and the vacuum degree reached 1x10 -3 Pa. After high-temperature sealing, it was placed in a muffle furnace, and the temperature was raised to 240°C at a rate of 10°C / h. After constant temperature for 120 hours, it was cooled to room temperature at a rate of 2°C / h. Thus, the polycrystalline powder of the compound SbH3P2O6was obtained.

[0057] Example 6

[0058] The compound SbH3P2O6was synthesized by room temperature solution method according to the reaction formula: Sb2O3+4H3PO3→2SbH3P2O6+3H2O:

[0059] Sb2O3, H3PO3 were mixed uniformly according to the molar ratio of 1:4, and then put into a clean plastic container. 20mL deionized water was added, and then ultrasonic treatment was performed to fully mix and dissolve. Filtration was performed with filter paper to obtain a mixed solution. The opening was sealed with a preservative film, and a plurality of small holes were made. After standing at a temperature of 50°C for 5 days, the polycrystalline powder of the compound SbH3P2O6was obtained.

[0060] Example 7

[0061] The compound SbH3P2O6was synthesized by room temperature solution method according to the reaction formula: Sb2O3+SbF3+6H3PO3→3SbH3P2O6+3HF+3H2O:

[0062] Sb2O3, SbF3, H3PO3 were mixed in a molar ratio of 1:1:6, put into a clean plastic container, 50 mL of deionized water was added, then ultrasonic treatment was used to make them fully mixed and dissolved, and a mixed solution was obtained by filtering with filter paper. The container was sealed with plastic wrap, a few small holes were made on the seal, and then the container was placed at a temperature of 40°C for 10 days to obtain a polycrystalline powder of compound SbH3P2O6.

[0063] Example 8

[0064] According to the reaction formula: SbF3+2H3PO3→SbH3P2O6+3HF, compound SbH3P2O6 was synthesized by a room temperature solution method:

[0065] SbF3, H3PO3 were mixed in a molar ratio of 1:2, put into a clean plastic container, 80 mL of deionized water was added, then ultrasonic treatment was used to make them fully mixed and dissolved, and a mixed solution was obtained by filtering with filter paper. The container was sealed with plastic wrap, a few small holes were made on the seal, and then the container was placed at a temperature of 45°C for 15 days to obtain a polycrystalline powder of compound SbH3P2O6.

[0066] Example 9

[0067] According to the reaction formula: Sb2O3+SbCl3+6H3PO3→3SbH3P2O6+3HCl+3H2O, compound SbH3P2O6 was synthesized by a room temperature solution method:

[0068] Sb2O3, SbCl3, H3PO3 were mixed in a molar ratio of 1:1:6, put into a clean plastic container, 100 mL of deionized water was added, then ultrasonic treatment was used to make them fully mixed and dissolved, and a mixed solution was obtained by filtering with filter paper. The container was sealed with plastic wrap, a few small holes were made on the seal, and then the container was placed at a temperature of 40°C for 20 days to obtain a polycrystalline powder of compound SbH3P2O6.

[0069] Example 10

[0070] According to the reaction formula: SbCl3+2H3PO3→SbH3P2O6+3HCl, compound SbH3P2O6 was synthesized by a room temperature solution method:

[0071] SbCl3, H3PO3 were mixed in a molar ratio of 1:2, put into a clean plastic container, 70 mL of deionized water was added, then ultrasonic treatment was used to make them fully mixed and dissolved, and a mixed solution was obtained by filtering with filter paper. The container was sealed with plastic wrap, a few small holes were made on the seal, and then the container was placed at a temperature of 40°C for 18 days to obtain a polycrystalline powder of compound SbH3P2O6.

[0072] Example 11

[0073] According to the reaction formula: Sb2O3+4H3PO3→2SbH3P2O6+3H2O, SbH3P2O6 nonlinear optical crystal is grown by hydrothermal method:

[0074] a. Sb2O3 and H3PO3 are mixed uniformly according to the molar ratio of 1:4, and are loaded into the inner liner of a 23ml reaction kettle. 15ml deionized water is added as a solvent. The mouth of the reaction kettle is tightly sealed, and is placed in an oven to be heated to 220°C at a rate of 20°C / h. After constant temperature for 24 hours, the temperature is decreased to room temperature at a rate of 2°C / h. Polycrystalline powder of SbH3P2O6 is obtained.

[0075] b. The polycrystalline powder of SbH3P2O6 obtained in step a is dissolved in deionized water, and is then ultrasonically treated to be fully mixed and dissolved. A mixed solution is obtained by filtering with filter paper.

[0076] c. The mixed solution obtained in step b is transferred into the inner liner of a clean and uncontaminated high-pressure reaction kettle with a volume of 100ml, and the reaction kettle is tightly sealed.

[0077] d. The high-pressure reaction kettle is placed in a constant temperature oven, and is heated to 180°C. After constant temperature for 5 days, the temperature is decreased to room temperature at a rate of 5°C / day. SbH3P2O6 nonlinear optical crystal with a size of 4mm×3mm×1mm is obtained.

[0078] Example 12

[0079] According to the reaction formula: Sb2O3+SbF3+6H3PO3→3SbH3P2O6+3HF+3H2O, SbH3P2O6 nonlinear optical crystal is grown by hydrothermal method:

[0080] a. Sb2O3, SbF3 and H3PO3 are mixed uniformly according to the molar ratio of 1:1:6, and are loaded into the inner liner of a 23ml reaction kettle. 15ml deionized water is added as a solvent. The mouth of the reaction kettle is tightly sealed, and is placed in an oven to be heated to 220°C at a rate of 20°C / h. After constant temperature for 36 hours, the temperature is decreased to room temperature at a rate of 2°C / h. Polycrystalline powder of SbH3P2O6 is obtained.

[0081] b. The polycrystalline powder of SbH3P2O6 obtained in step a is dissolved in deionized water, and is then ultrasonically treated to be fully mixed and dissolved. A mixed solution is obtained by filtering with filter paper.

[0082] c. The mixed solution obtained in step b is transferred into the inner liner of a clean and uncontaminated high-pressure reaction kettle with a volume of 100ml, and the reaction kettle is tightly sealed.

[0083] d, the high-pressure reactor is placed in a thermostat, and is raised to 200°C, and is kept at this temperature for 6 days, and is then cooled to room temperature at a rate of 15°C / day, to obtain SbH3P2O6 nonlinear optical crystal with a size of 3mm x 2mm x 1mm.

[0084] Example 13

[0085] SbH3P2O6 nonlinear optical crystal is grown by a hydrothermal method according to the reaction formula: SbF3 + 2H3PO3→ SbH3P2O6 + 3HF.

[0086] a, SbF3 and H3PO3 are mixed uniformly at a molar ratio of 1:2, and are loaded into the inner lining of a 100ml reactor, 15ml of deionized water is added as a solvent, the mouth of the reactor is tightly sealed, and is placed in an oven and heated to 220°C at a rate of 20°C / h, and is kept at this temperature for 72 hours, and is then cooled to room temperature at a rate of 2°C / h, to obtain SbH3P2O6 polycrystalline powder.

[0087] b, the SbH3P2O6 polycrystalline powder obtained in step a is dissolved in deionized water, and is then ultrasonically treated to fully mix and dissolve, and is filtered with filter paper to obtain a mixed solution;

[0088] c, the mixed solution obtained in step b is transferred to the inner lining of a clean and uncontaminated high-pressure reactor with a volume of 100ml, and the reactor is tightly sealed;

[0089] d, the high-pressure reactor is placed in a thermostat, and is raised to 200°C, and is kept at this temperature for 6 days, and is then cooled to room temperature at a rate of 10°C / day, to obtain SbH3P2O6 nonlinear optical crystal with a size of 4mm x 2mm x 2mm.

[0090] Example 14

[0091] SbH3P2O6 nonlinear optical crystal is grown by a hydrothermal method according to the reaction formula: Sb2O3 + SbCl3 + 6H3PO3→ 3SbH3P2O6 + 3HCl + 3H2O.

[0092] a, Sb2O3, SbCl3 and H3PO3 are mixed uniformly at a molar ratio of 1:1:6, and are loaded into the inner lining of a 23ml reactor, 15ml of deionized water is added as a solvent, the mouth of the reactor is tightly sealed, and is placed in an oven and heated to 220°C at a rate of 20°C / h, and is kept at this temperature for 120 hours, and is then cooled to room temperature at a rate of 2°C / h, to obtain SbH3P2O6 polycrystalline powder;

[0093] b, the SbH3P2O6 polycrystalline powder obtained in step a is dissolved in deionized water, and is then ultrasonically treated to fully mix and dissolve, and is filtered with filter paper to obtain a mixed solution;

[0094] c, the mixed solution obtained in step b is transferred into a clean and uncontaminated inner liner of a high-pressure reaction kettle with a volume of 100 mL, and the reaction kettle is tightly sealed by screwing;

[0095] d, the high-pressure reaction kettle is placed in a thermostat, raised to 210°C, and kept at constant temperature for 7 days, and then cooled to room temperature at a rate of 18°C / day, to obtain SbH3P2O6 nonlinear optical crystal with a size of 5 mm x 3 mm x 1 mm.

[0096] Example 15

[0097] According to the reaction formula: SbCl3 + 2H3PO3 → SbH3P2O6 + 3HCl, SbH3P2O6 nonlinear optical crystal is grown by hydrothermal method:

[0098] a, SbCl3 and H3PO3 are mixed uniformly in a molar ratio of 1:2, and are loaded into the inner liner of a 23 ml reaction kettle, 15 mL of deionized water is added as solvent, the mouth of the reaction kettle is tightly sealed and placed in an oven to raise the temperature to 220°C at a rate of 20°C / h, and then kept at constant temperature for 72 hours, and then cooled to room temperature at a rate of 2°C / h, to obtain polycrystalline powder of SbH3P2O6;

[0099] b, the polycrystalline powder of SbH3P2O6 obtained in step a is dissolved in deionized water, and then ultrasonic treatment is performed to fully mix and dissolve, and a filter paper is used to filter to obtain a mixed solution;

[0100] c, the mixed solution obtained in step b is transferred into a clean and uncontaminated inner liner of a high-pressure reaction kettle with a volume of 100 mL, and the reaction kettle is tightly sealed by screwing;

[0101] d, the high-pressure reaction kettle is placed in a thermostat, raised to 250°C, and kept at constant temperature for 8 days, and then cooled to room temperature at a rate of 25°C / day, to obtain SbH3P2O6 nonlinear optical crystal with a size of 4 mm x 4 mm x 2 mm.

[0102] Example 16

[0103] SbH3P2O6 nonlinear optical crystal is grown by vacuum packaging method:

[0104] The polycrystalline powder of compound SbH3P2O6 obtained in Example 1 is mixed uniformly with the cosolvent H3PO3 in a molar ratio of 1:0.1, and is loaded into a graphite crucible, and then the graphite crucible is placed in a Φ40 mm quartz tube, the quartz tube is vacuumed to a vacuum degree of 1 x 10 -3 Pa, and after high-temperature sealing, it is placed in a muffle furnace, raised to 220°C, kept at constant temperature for 72 hours, and then cooled to room temperature at a rate of 1°C / h, to obtain SbH3P2O6 nonlinear optical crystal with a size of 2 mm x 2 mm x 1 mm.

[0105] Example 17

[0106] SbH3P2O6 nonlinear optical crystal was grown by vacuum encapsulation method:

[0107] SbH3P2O6 polycrystalline powder obtained in Example 2 was mixed with cosolvent H3PO3 at a molar ratio of 1:0.5, and was 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 x 10 - 3 After high-temperature sealing, Pa was placed in a muffle furnace, and was heated to 200°C. After constant temperature for 120 hours, it was cooled to room temperature at a rate of 0.1°C / h, and a 4 mm x 3 mm x 2 mm SbH3P2O6 nonlinear optical crystal was obtained.

[0108] Example 18

[0109] SbH3P2O6 nonlinear optical crystal was grown by vacuum encapsulation method:

[0110] SbH3P2O6 polycrystalline powder obtained in Example 3 was mixed with cosolvent H3PO3 at a molar ratio of 1:1, and was 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 x 10 -3 After high-temperature sealing, it was placed in a muffle furnace, and was heated to 210°C. After constant temperature for 24 hours, it was cooled to room temperature at a rate of 1°C / h, and a SbH3P2O6 nonlinear optical crystal was obtained.

[0111] Example 19

[0112] SbH3P2O6 nonlinear optical crystal was grown by vacuum encapsulation method:

[0113] SbH3P2O6 polycrystalline powder obtained in Example 4 was mixed with cosolvent H3PO3 at a molar ratio of 1:4, and was 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 x 10 -3 After high-temperature sealing, it was placed in a muffle furnace, and was heated to 230°C. After constant temperature for 80 hours, it was cooled to room temperature at a rate of 2°C / h, and a 3 mm x 3 mm x 2 mm SbH3P2O6 nonlinear optical crystal was obtained.

[0114] Example 20

[0115] SbH3P2O6 nonlinear optical crystal was grown by vacuum encapsulation method:

[0116] The SbH3P2O6 polycrystalline powder obtained in Example 5 was mixed with the cosolvent H3PO3 at a molar ratio of 1:6, and was loaded into a graphite crucible, which was then placed in a Φ40 mm quartz tube. The quartz tube was evacuated to a vacuum degree of 1 x 10 -3 Pa, and was placed in a muffle furnace after high-temperature sealing, and was heated to 250°C, and was kept at this temperature for 100 hours, and then was decreased to room temperature at a rate of 3°C / h, to obtain a 3 mm x 2 mm x 1 mm SbH3P2O6 nonlinear optical crystal.

[0117] Example 21

[0118] The SbH3P2O6 nonlinear optical crystal was grown by a room-temperature solution method:

[0119] The 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 filtration was performed with filter paper to obtain a mixed solution;

[0120] The obtained mixed solution was placed in a clean plastic container, was sealed with weighing paper, and was placed in a static environment without shaking, pollution, and air convection, a plurality of small holes were punched in the sealing to adjust the evaporation rate of water in the aqueous solution, and was left to stand at 40°C for 20 days;

[0121] After crystal particles grew on the bottom of the container, until the size of the crystal particles no longer changed obviously, a seed crystal was obtained;

[0122] A good quality seed crystal was selected, was hung in the prepared mixed solution, and was left to stand to grow at a temperature of 40°C for 30 days, to obtain a SbH3P2O6 nonlinear optical crystal with a size of 8 mm x 8 mm x 6 mm.

[0123] Example 22

[0124] The SbH3P2O6 nonlinear optical crystal was grown by a room-temperature solution method:

[0125] 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, and filtration was performed with filter paper to obtain a mixed solution;

[0126] The obtained mixed solution was placed in a clean plastic container, was sealed with weighing paper, and was placed in a static environment without shaking, pollution, and air convection, a plurality of small holes were punched in the sealing to adjust the evaporation rate of water in the aqueous solution, and was left to stand at 45°C for 10 days;

[0127] After crystal particles grew on the bottom of the container, until the size of the crystal particles no longer changed obviously, a seed crystal was obtained;

[0128] The good quality seed crystal is selected, and is hung in the prepared mixed solution, and is placed to grow at 45°C for 10 days, so that SbH3P2O6 nonlinear optical crystal with size of 8mmx7mmx3mm is obtained.

[0129] Example 23

[0130] SbH3P2O6 nonlinear optical crystal is grown by room temperature solution method:

[0131] The SbH3P2O6 polycrystal powder obtained in Example 8 is put into a cleaned plastic container, 50mL deionized water is added, and then ultrasonic treatment is carried out to fully mix and dissolve, and filtration is carried out with filter paper, so that a mixed solution is obtained;

[0132] The obtained mixed solution is placed in a clean plastic container, is sealed with weighing paper, and is placed in a static environment without shaking, pollution and air convection, a plurality of small holes are punched on the sealing to adjust the evaporation rate of water in the aqueous solution, and is placed to stand for 12 days at 48°C;

[0133] After the solution grows into crystal particles at the bottom of the container, until the size of the crystal particles no longer changes obviously, a seed crystal is obtained;

[0134] The good quality seed crystal is selected, and is hung in the prepared mixed solution, and is placed to grow at 42°C for 20 days, so that SbH3P2O6 nonlinear optical crystal with size of 9mmx6mmx2mm is obtained.

[0135] Example 24

[0136] SbH3P2O6 nonlinear optical crystal is grown by room temperature solution method:

[0137] The SbH3P2O6 polycrystal powder obtained in Example 9 is put into a cleaned plastic container, 80mL deionized water is added, and then ultrasonic treatment is carried out to fully mix and dissolve, and filtration is carried out with filter paper, so that a mixed solution is obtained;

[0138] The obtained mixed solution is placed in a clean plastic container, is sealed with weighing paper, and is placed in a static environment without shaking, pollution and air convection, a plurality of small holes are punched on the sealing to adjust the evaporation rate of water in the aqueous solution, and is placed to stand for 5 days at 50°C;

[0139] After the solution grows into crystal particles at the bottom of the container, until the size of the crystal particles no longer changes obviously, a seed crystal is obtained;

[0140] The good quality seed crystal is selected, and is hung in the prepared mixed solution, and is placed to grow at 50°C for 30 days, so that SbH3P2O6 nonlinear optical crystal with size of 9mmx7mmx6mm is obtained.

[0141] Example 25

[0142] SbH3P2O6 nonlinear optical crystals were grown using a room temperature solution method.

[0143] 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. The mixture was then filtered with filter paper to obtain a mixed solution.

[0144] Place the obtained mixed solution in a clean plastic container, seal it with weighing paper, and place it in a static environment without shaking, pollution, or air convection. Make several small holes in the seal to adjust the evaporation rate of water in the aqueous solution, and let it stand at 45°C for 12 days.

[0145] Seed crystals are obtained when crystal particles grow at the bottom of the container and the size of the crystal particles no longer changes significantly.

[0146] Select high-quality seed crystals, suspend them in the prepared mixed solution, and let them grow at 45℃ for 20 days to obtain SbH3P2O6 nonlinear optical crystals with dimensions of 6mm×5mm×5mm.

[0147] Example 26

[0148] The arbitrary SbH3P2O6 crystals obtained in Examples 11-25 were processed according to matching directions, and then... Figure 3 As shown, the SbH3P2O6 single crystal 3 is positioned at location 3. At room temperature, a Q-switched Nd:YAG laser is used as the light source with an incident wavelength of 1064nm. An infrared beam 2 with a wavelength of 1064nm is emitted from the Q-switched Nd:YAG laser 1 and enters the SbH3P2O6 single crystal 3, producing green frequency-doubled light with a wavelength of 532nm. The output intensity is approximately twice that of KDP under the same conditions.

Claims

1. A nonlinear optical crystal of antimony phosphite, characterized in that... The crystal has the chemical formula SbH3P2O6, a molecular weight of 282.7, belongs to the monoclinic crystal system, and its space group is [space group number missing]. 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°, unit cell volume is 294.29(8) Å 3 .

2. The method for preparing the antimony phosphite nonlinear optical crystal as described in claim 1, characterized in that... Crystals are grown using hydrothermal methods, vacuum encapsulation methods, or room temperature solution methods. The hydrothermal growth of the antimony phosphite nonlinear optical crystal is carried out according to the following steps: a. Mix the Sb-containing compound and the P-containing compound evenly in a molar ratio of Sb:P = 1:2, and place the mixture into the lining of a 23 ml reaction vessel. Add deionized water as a solvent, place the vessel in an oven, raise the temperature to 220 °C at a rate of 20 °C / h, and hold the temperature for 24-120 hours. Then, cool the mixture to room temperature at a rate of 2 °C / h to obtain SbH3P2O6 polycrystalline powder. The Sb-containing compound is Sb2O3, SbF3, or SbCl3; the P-containing compound is H3PO3. b. Dissolve the SbH3P2O6 polycrystalline powder obtained in step a in deionized water, then treat it with ultrasound to ensure thorough mixing and dissolution, and filter it with filter paper to obtain a mixed solution. c. Transfer the mixed solution obtained in step b into the liner of a clean, uncontaminated 100 mL high-pressure reactor, and tighten and seal the reactor. d. Place the high-pressure reactor in a constant temperature chamber, raise it to 180-250 ℃, keep it at the temperature for 5-8 days, and then cool it down to room temperature at a cooling rate of 5-25 ℃ / day to obtain the SbH3P2O6 nonlinear optical crystal. The vacuum encapsulation method for growing antimony phosphite nonlinear optical crystals is specifically performed according to the following steps: a. Mix the Sb-containing compound and the P-containing compound evenly in a molar ratio of Sb:P = 1:2, and place the mixture into the lining of a 23 ml reaction vessel. Add deionized water as a solvent, and place the vessel in an oven to heat to 220 °C and maintain the temperature for 24-120 hours to obtain SbH3P2O6 polycrystalline powder. The Sb-containing compound is Sb2O3, SbF3, or SbCl3; the P-containing compound is H3PO3. b. Mix the SbH3P2O6 polycrystalline powder obtained in step a with the co-solvent at a molar ratio of 0.1:0.1-6 until homogeneous, ensuring the amount of SbH3P2O6 polycrystalline powder is not zero. Place the mixture into a graphite crucible, then place the graphite crucible into a quartz tube. Evacuate the quartz tube to a vacuum level of 1×10⁻⁶. −3 Pa, after being sealed at high temperature, is placed in a muffle furnace, heated to 200-250 °C, held at that 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 for growing antimony phosphite nonlinear optical crystals using the room temperature solution method is as follows: a. Mix the Sb-containing compound and the P-containing compound evenly in a molar ratio of Sb:P = 1:2, and place the mixture into the lining of a 23 ml reaction vessel. Add deionized water as a solvent, and place the vessel in an oven to heat to 220 °C and maintain the temperature for 24-120 hours to obtain SbH3P2O6 polycrystalline powder. The Sb-containing compound is Sb2O3, SbF3, or SbCl3; 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, then sonicate to fully mix and dissolve, filter 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, and place it in a static environment without shaking, pollution, or air convection. Make several small holes in the seal to adjust the evaporation rate of water in the aqueous solution. Let it stand at 40-50 ℃ for 5-20 days. d. After the solution in step c grows crystal particles at the bottom of the container until the size of the crystal particles no longer changes significantly, seed crystals are obtained. e. Select the seed crystal with better quality from step d, suspend it in the mixed solution prepared in step b, and let it grow at a temperature of 40-50℃ for 10-30 days to obtain SbH3P2O6 nonlinear optical crystal.

3. The use of the antimony phosphite nonlinear optical crystal as described in claim 1 in preparing second and third harmonic output of the 1064 nm fundamental frequency light output by an Nd:YAG laser.

4. The use of the antimony phosphite nonlinear optical crystal as described in claim 1 in the preparation of green frequency-doubled light output with a wavelength of 532 nm.

5. The use of the antimony phosphite nonlinear optical crystal as described in claim 1 in the fabrication of a frequency multiplier, an up or down frequency converter, or an optical parametric oscillator.

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