Compound potassium borosilicate and potassium borosilicate nonlinear optical crystal and preparation method and use

Abstract

This invention discloses potassium borosilicate, potassium borosilicate nonlinear optical crystals, their preparation methods, and applications, belonging to the field of nonlinear optical crystal technology. The chemical formula of potassium borosilicate is K4B6Si3O. 17 With a molecular weight of 577.53, it was prepared using solid-state synthesis or vacuum encapsulation; the chemical formula of this crystal is K4B6Si3O. 17 It has a molecular weight of 577.53, belongs to the monoclinic crystal system, and has a space group of C 2. The unit cell parameters are a =11.8628(13)Å, b =6.6285(6)Å, c =11.0097(19)Å, β =117.183(4)°, unit cell volume is 770.10(17) Å. 3 The powder frequency doubling effect of the crystal is about 1.4 times that of KH2PO4 (KDP), and the ultraviolet absorption edge is shorter than 190 nm. The crystal has good chemical stability and can be used as an ultraviolet and deep ultraviolet nonlinear optical crystal in all-solid-state lasers.

Description

Technical Field

[0001] This invention belongs to the field of nonlinear optical crystal technology, and particularly relates to potassium borosilicate compound and potassium borosilicate nonlinear optical crystal, as well as their preparation methods and applications. Background Technology

[0002] Ultraviolet (UV) or deep ultraviolet (DUV) nonlinear optical (NLO) materials play a crucial role in laser frequency conversion, photolithography, and semiconductor photolithography. Because they can generate coherent UV or DUV light, scientists have invented several NLO crystals in the UV and DUV bands over the past few decades, including… β -BaB2O4(BBO), LiB3O5(LBO), CsB3O5(CBO), CsLiB6O 10 (CLBO), KBe2BO3F2(KBBF), K3B6O 10 Cl(KBOC), etc. As is well known, the only practical deep-ultraviolet nonlinear optical crystal currently is the KBe2BO3F2 (KBBF) crystal invented by Chinese scientists. This crystal has a layered growth habit, making it difficult to grow large-size crystals, which to some extent limits its application. Scientists from various countries are still paying close attention to the exploration and research of various novel nonlinear optical crystals, focusing not only on the optical and mechanical properties of crystals, but also increasingly emphasizing the fabrication characteristics of crystals. Summary of the Invention

[0003] To address the aforementioned technical problems, this invention proposes the compound potassium borosilicate and potassium borosilicate nonlinear optical crystals, along with their preparation methods and applications.

[0004] To achieve the above objectives, the present invention provides the following technical solution: This invention provides a compound, potassium borosilicate, with the chemical formula K4B6Si3O. 17 Its molecular weight is 577.53.

[0005] The present invention also provides a method for preparing the above-mentioned compound potassium borosilicate by means of solid-phase synthesis or vacuum encapsulation. When preparing potassium borosilicate using a solid-phase synthesis method, the steps are as follows: A K-containing compound, a B-containing compound, and a Si-containing compound are mixed evenly in a molar ratio of K:B:Si = 4:6:3. The mixture is then placed in a platinum crucible and heated in a muffle furnace to 550-850 °C, where it is held at that temperature for 24-120 hours to obtain potassium borosilicate (K4B6Si3O). 17 ); When preparing potassium borosilicate using the vacuum encapsulation method, the steps are as follows: The K-containing compound, B-containing compound, and Si-containing compound were mixed evenly in a molar ratio of K:B:Si = 4:6:3, and the mixture was placed into a quartz tube. The quartz tube was then evacuated to a vacuum level of 1 × 10⁻⁶. -3 After being sealed at high temperature, the compound K4B6Si3O was placed in a muffle furnace and heated to 600-850 °C at a rate of 5-10 °C / h, and held at that temperature for 24-120 hours to obtain the compound K4B6Si3O. 17 .

[0006] Furthermore, in the preparation method of potassium borosilicate, the K-containing compound is selected from KOH, K2CO3, KNO3, KHCO3 or K2SiO3; the B-containing compound is H3BO3 or B2O3; and the Si-containing compound is SiO2 or H2SiO3.

[0007] This invention also provides a potassium borosilicate nonlinear optical crystal with the chemical formula K4B6Si3O. 17 It has a molecular weight of 577.53, belongs to the monoclinic crystal system, and has a space group of C 2. The unit cell parameters are a = 11.8628(13) Å, b = 6.6285(6)Å, c = 11.0097(19) Å, β = 117.183(4)°, unit cell volume is 770.10(17) Å 3 The powder doubling effect of this crystal is about 1.4 times that of KH2PO4(KDP), and the ultraviolet absorption edge is shorter than 190 nm.

[0008] The present invention also provides a method for preparing the above-mentioned potassium borosilicate nonlinear optical crystal, wherein the crystal is grown by melt method, high temperature melt method, vacuum encapsulation method, hydrothermal method or room temperature solution method; When growing potassium borosilicate nonlinear optical crystals using the melt method, the specific operation is as follows: a. Mix the K-containing compound, the B-containing compound, and the Si-containing compound in a molar ratio of K:B:Si = 4:6:3 until homogeneous. Place the mixture in a platinum crucible and heat it in a muffle furnace to 700-900 °C. Maintain the temperature for 24-120 hours to obtain the compound K4B6Si3O. 17 powder; b. The compound K4B6Si3O prepared in step a. 17 The powder is placed in a platinum crucible, placed in a muffle furnace, heated to 700-900 ℃, and held at that temperature for 10-120 hours to obtain a mixed melt. c. The mixed melt obtained in step b is slowly cooled to 650 °C at a rate of 0.1-2 °C / h, and then rapidly cooled to room temperature at a rate of 5-10 °C / h to obtain K4B6Si3O 17 Seed crystal; d. Crystal growth in the compound melt using the Czochralski method: The K4B6Si3O obtained in step c is grown in the compound melt. 17 The seed crystal is fixed on a seed crystal rod and lowered above the mixed melt obtained in step b. A crystal rotation of 2-20 rpm is applied using a crystal growth controller, and the seed crystal is pulled up at a rate of 1-10 mm / day while simultaneously cooling at a rate of 0.1-10 ℃ / h. Once crystal growth stops, K4B6Si3O is obtained. 17 Nonlinear optical crystals; Alternatively, crystals can be grown in the compound melt using the Czochralski method: The K4B6Si3O obtained in step c... 17 The seed crystal is fixed on a seed crystal rod and lowered above the mixed melt obtained in step b. The temperature is lowered at a rate of 0.1-10 ℃ / h to allow the crystal to grow for 5-15 hours. The crystal is then slowly raised without leaving the liquid surface to continue growth. This process is repeated until the crystal growth stops, at which point K4B6Si3O is obtained. 17 Nonlinear optical crystals; Alternatively, crystals can be grown in the compound melt using the crucible lowering method: K4B6Si3O prepared in step c... 17 The seed crystal is placed at the bottom of the crucible, and then the compound K4B6Si3O prepared in step a is added. 17 The powder is placed in a crucible, which is then sealed with platinum. The growth furnace temperature is raised to 700-900 °C and held constant for 10-120 hours. The crucible position is adjusted to allow the seed crystal to slightly melt. The crucible is then lowered at a rate of 1-10 mm / day while maintaining the growth temperature, or lowered to 650 °C at the fastest possible cooling rate of 3 °C / h. After growth is complete, the temperature is rapidly reduced to room temperature at a rate of 5-10 °C / h to obtain K4B6Si3O. 17 Nonlinear optical crystals; When growing potassium borosilicate nonlinear optical crystals using the high-temperature melt method, the specific operation is as follows: a. Mix the K-containing compound, the B-containing compound, and the Si-containing compound in a molar ratio of K:B:Si = 4:6:3 until homogeneous. Place the mixture in a platinum crucible and heat it in a muffle furnace to 700-900 °C. Maintain the temperature for 24-120 hours to obtain the compound K4B6Si3O. 17 powder; b. The compound K4B6Si3O obtained in step a. 17The powder and flux are mixed evenly at a molar ratio of 1:(0.1-6), then placed in a platinum crucible, heated to 700-900 ℃, and kept at the temperature for 5-120 hours to obtain a mixed melt. c. Seed crystal preparation: The mixed melt obtained in step b is placed in a single crystal furnace and slowly cooled to 650 ℃ at a rate of 0.1-2 ℃ / h, then rapidly cooled to room temperature at a rate of 5-10 ℃ / h to obtain K4B6Si3O 17 Seed crystal; d. Crystal growth: The K4B6Si3O obtained in step c is grown into a crystal. 17 The seed crystal is fixed on a seed crystal rod and lowered from above the mixed melt obtained in step b. A crystal rotation of 2-20 rpm is applied using a crystal growth controller, and the temperature is lowered at a rate of 0.1-3 ℃ / h. Once crystal growth stops, K4B6Si3O is obtained. 17 Nonlinear optical crystals; When growing potassium borosilicate nonlinear optical crystals using the vacuum encapsulation method, the specific operation is as follows: a. Mix the K-containing compound, the B-containing compound, and the Si-containing compound in a molar ratio of K:B:Si = 4:6:3 until homogeneous. Place the mixture in a platinum crucible and heat it in a muffle furnace to 650-850 °C. Maintain the temperature for 24-120 hours to obtain the compound K4B6Si3O. 17 powder; b. The compound K4B6Si3O obtained in step a. 17 The powder and flux are mixed evenly at a molar ratio of (0.1-1):(0.1-6), placed in a quartz tube, sealed at high temperature, and then placed in a muffle furnace. The temperature is raised to 650-850 ℃ and held for 5-120 hours. Then, the temperature is lowered to 650 ℃ at a rate of 0.1-3 ℃ / h, and then rapidly cooled to room temperature at a rate of 5-10 ℃ / h to obtain K4B6Si3O. 17 Nonlinear optical crystals; When growing potassium borosilicate nonlinear optical crystals using the hydrothermal method, the specific operation is as follows: a. Mix the K-containing compound, the B-containing compound, and the Si-containing compound in a molar ratio of K:B:Si = 4:6:3 until homogeneous. Place the mixture in a platinum crucible and heat it in a muffle furnace to 600-850 °C. Maintain the temperature for 24-120 hours to obtain the compound K4B6Si3O. 17 powder; b. The compound K4B6Si3O obtained in step a. 17 The powder was dissolved in water. The incompletely dissolved mixture was ultrasonically treated at 60 °C to ensure it was fully mixed and dissolved. The pH was adjusted to 8-11 with HF and KOH 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 the temperature to 450-600 ℃, maintain the temperature for 5-8 days, and then cool it down to room temperature at a rate of 5-20 ℃ / day to obtain K4B6Si3O. 17 Nonlinear optical crystals; When growing potassium borosilicate nonlinear optical crystals using the room temperature solution method, the specific operation is as follows: a. Mix the K-containing compound, the B-containing compound, and the Si-containing compound in a molar ratio of K:B:Si = 4:6:3 until homogeneous. Place the mixture in a platinum crucible and heat it in a muffle furnace to 700-900 °C. Maintain the temperature for 24-120 hours to obtain the compound K4B6Si3O. 17 powder; b. The compound K4B6Si3O obtained in step a. 17 Place the powder in a clean glass container, add 20-100 mL of water, and then sonicate to fully mix and dissolve. Adjust the pH to 8-11 with HF and KOH, and filter with filter paper to obtain a mixed solution. c. Place the mixed solution obtained in step b in a clean glass 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 the water in the aqueous solution. Let it stand at room temperature for 5-20 days. d. When crystal particles grow at the bottom of the container from the solution in step c, until the size of the crystal particles no longer changes significantly, seed crystals are obtained. e. Select a clean, smooth, uncontaminated, and crack-free seed crystal from step d, suspend it in the mixed solution prepared in step b, and allow it to grow at room temperature for 10-30 days to obtain K4B6Si3O. 17 Nonlinear optical crystals.

[0009] Furthermore, in the preparation method of potassium borosilicate nonlinear optical crystal, the K-containing compound is selected from KOH, K2CO3, KNO3, KHCO3 or K2SiO3; the B-containing compound is H3BO3 or B2O3; and the Si-containing compound is SiO2 or H2SiO3.

[0010] Furthermore, in the preparation method of potassium borosilicate nonlinear optical crystal, the flux is selected from H3BO3, B2O3, PbO or PbF2.

[0011] The present invention also provides the use of the above-mentioned potassium borosilicate nonlinear optical crystal in the preparation of frequency multiplier generators, up or down frequency converters or optical parametric oscillators.

[0012] The present invention also provides the use of the above-mentioned potassium borosilicate nonlinear optical crystal in the preparation of second, third, fourth and fifth harmonic output of the 1064 nm fundamental frequency light output by the Nd:YAG laser.

[0013] The present invention also provides the use of the above-mentioned potassium borosilicate nonlinear optical crystal in the preparation of deep ultraviolet frequency-doubled light output below 200 nm.

[0014] Compared with the prior art, the present invention has the following advantages and technical effects: Potassium borosilicate (K4B6Si3O) with centimeter-sized particles was obtained using the method of this invention. 17 Nonlinear optical crystals, by using large-sized crucibles or containers and extending the crystal growth period, can be produced to obtain correspondingly large-sized nonlinear optical crystals, such as K4B6Si3O. 17 In the K4B6Si3O 17 Nonlinear optical crystals are easy to grow into transparent, unencapsulated crystals, and have advantages such as fast growth rate, low cost, and easy acquisition of large-size crystals.

[0015] Large-sized K4B6Si3O obtained by the preparation method of the present invention 17 Nonlinear optical crystals are produced by orienting a crystal blank according to its crystallographic data, cutting the crystal to the required angle, thickness, and cross-sectional dimensions, and polishing the light-transmitting surface of the crystal. This allows it to be used as a nonlinear optical device. (K4B6Si3O) 17 Nonlinear optical crystals have advantages such as transmission bands reaching the deep ultraviolet region, stable physicochemical properties, resistance to deliquescence, and ease of processing and storage. Attached Figure Description

[0016] The accompanying drawings, which form part of this invention, are used to provide a further understanding of the invention. The illustrative embodiments of the invention and their descriptions are used to explain the invention and do not constitute an undue limitation of the invention. In the drawings: Figure 1 The compound K4B6Si3O in Example 1 of this invention 17 XRD pattern of the powder; Figure 2 K4B6Si3O in Embodiment 45 of the present invention 17 Structure diagram of a nonlinear optical crystal; Figure 3 To utilize the K4B6Si3O of this invention 17 A schematic diagram illustrating the working principle of a nonlinear optical device fabricated from a nonlinear optical crystal, where 1 represents the laser, 2 represents the emitted beam, and 3 represents K4B6Si3O. 17 Nonlinear optical crystal, 4 is the outgoing beam, 5 is the filter. Detailed Implementation

[0017] Various exemplary embodiments of the present invention will now be described in detail. This detailed description should not be considered as a limitation of the present invention, but rather as a more detailed description of certain aspects, features, and embodiments of the present invention.

[0018] It should be understood that the terminology used in this invention is merely for describing particular embodiments and is not intended to limit the invention. Furthermore, with respect to numerical ranges in this invention, it should be understood that each intermediate value between the upper and lower limits of the range is also specifically disclosed. Every smaller range between any stated value or intermediate value within a stated range, and any other stated value or intermediate value within said range, is also included in this invention. The upper and lower limits of these smaller ranges may be independently included or excluded from the range.

[0019] Unless otherwise stated, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art. While only preferred methods and materials have been described herein, any methods and materials similar or equivalent to those described herein may be used in the implementation or testing of this invention. All references to this specification are incorporated by way of citation to disclose and describe methods and / or materials associated with those references. In the event of any conflict with any incorporated reference, the content of this specification shall prevail.

[0020] Various modifications and variations can be made to the specific embodiments described in this specification without departing from the scope or spirit of the invention, as will be apparent to those skilled in the art. Other embodiments derived from this specification will also be apparent to those skilled in the art. This specification and embodiments are merely exemplary.

[0021] The terms “include,” “including,” “have,” “contain,” etc., used in this article are all open-ended terms, meaning that they include but are not limited to.

[0022] An embodiment of the present invention provides a compound, potassium borosilicate, with the chemical formula K4B6Si3O. 17 Its molecular weight is 577.53.

[0023] The embodiments of the present invention also provide a method for preparing the above-mentioned compound potassium borosilicate, which is prepared by solid-phase synthesis or vacuum encapsulation. When preparing potassium borosilicate using a solid-phase synthesis method, the steps are as follows: A K-containing compound, a B-containing compound, and a Si-containing compound are mixed evenly in a molar ratio of K:B:Si = 4:6:3, placed in a platinum crucible, and heated in a muffle furnace to 550-850 °C and held at that temperature for 24-120 hours to obtain the compound K4B6Si3O.17 ; When preparing potassium borosilicate using the vacuum encapsulation method, the steps are as follows: The K-containing compound, B-containing compound, and Si-containing compound were mixed evenly in a molar ratio of K:B:Si = 4:6:3, and the mixture was placed into a quartz tube. The quartz tube was then evacuated to a vacuum level of 1 × 10⁻⁶. -3 After being sealed at high temperature, the compound K4B6Si3O was placed in a muffle furnace and heated to 600-850 °C at a rate of 5-10 °C / h, and held at that temperature for 24-120 hours to obtain the compound K4B6Si3O. 17 .

[0024] In a preferred embodiment of the present invention, in the method for preparing potassium borosilicate, the K-containing compound is selected from KOH, K2CO3, KNO3, KHCO3 or K2SiO3; the B-containing compound is H3BO3 or B2O3; and the Si-containing compound is SiO2 or H2SiO3.

[0025] An embodiment of the present invention also provides a potassium borosilicate nonlinear optical crystal with the chemical formula K4B6Si3O. 17 It has a molecular weight of 577.53, belongs to the monoclinic crystal system, and has a space group of C 2. The unit cell parameters are a = 11.8628(13) Å, b =6.6285(6) Å, c = 11.0097(19) Å, β = 117.183(4)°, unit cell volume is 770.10(17) Å 3 The powder frequency doubling effect of this crystal is about 1.4 times that of KH2PO4(KDP), and the ultraviolet absorption edge is shorter than 190 nm. This crystal has good chemical stability and can be used as an ultraviolet and deep ultraviolet nonlinear optical crystal in all-solid-state lasers.

[0026] The embodiments of the present invention also provide a method for preparing the above-mentioned potassium borosilicate nonlinear optical crystal, wherein the crystal is grown by melt method, high temperature melt method, vacuum encapsulation method, hydrothermal method or room temperature solution method; When growing potassium borosilicate nonlinear optical crystals using the melt method, the specific operation is as follows: a. Mix the K-containing compound, the B-containing compound, and the Si-containing compound in a molar ratio of K:B:Si = 4:6:3 until homogeneous. Place the mixture in a platinum crucible and heat it in a muffle furnace to 700-900 °C. Maintain the temperature for 24-120 hours to obtain the compound K4B6Si3O. 17The powder contains K compounds selected from KOH, K2CO3, KNO3, KHCO3, or K2SiO3; B compounds are H3BO3 or B2O3; and Si compounds are SiO2 or H2SiO3. b. The compound K4B6Si3O prepared in step a. 17 The powder is placed in a platinum crucible, placed in a muffle furnace, heated to 700-900 ℃, and held at that temperature for 10-120 hours to obtain a mixed melt. c. The mixed melt obtained in step b is slowly cooled to 650 °C at a rate of 0.1-2 °C / h, and then rapidly cooled to room temperature at a rate of 5-10 °C / h to obtain K4B6Si3O 17 Seed crystal; d. Crystal growth in the compound melt using the Czochralski method: The K4B6Si3O obtained in step c is grown in the compound melt. 17 The seed crystal is fixed on a seed crystal rod and lowered above the mixed melt obtained in step b. A crystal rotation of 2-20 rpm is applied using a crystal growth controller, and the seed crystal is pulled up at a rate of 1-10 mm / day while simultaneously cooling at a rate of 0.1-10 ℃ / h. Once crystal growth stops, K4B6Si3O is obtained. 17 Nonlinear optical crystals; Alternatively, crystals can be grown in the compound melt using the Czochralski method: The K4B6Si3O obtained in step c... 17 The seed crystal is fixed on a seed crystal rod and lowered above the mixed melt obtained in step b. The temperature is lowered at a rate of 0.1-10 ℃ / h to allow the crystal to grow for 5-15 hours. The crystal is then slowly raised without leaving the liquid surface to continue growth. This process is repeated until the crystal growth stops, at which point K4B6Si3O is obtained. 17 Nonlinear optical crystals; Alternatively, crystals can be grown in the compound melt using the crucible lowering method: K4B6Si3O prepared in step c... 17 The seed crystal is placed at the bottom of the crucible, and then the compound K4B6Si3O prepared in step a is added. 17 The powder is placed in a crucible, which is then sealed with platinum. The growth furnace temperature is raised to 700-900 °C and held constant for 10-120 hours. The crucible position is adjusted to allow the seed crystal to slightly melt. The crucible is then lowered at a rate of 1-10 mm / day while maintaining the growth temperature, or lowered to 650 °C at the fastest possible cooling rate of 3 °C / h. After growth is complete, the temperature is rapidly reduced to room temperature at a rate of 5-10 °C / h to obtain K4B6Si3O. 17 Nonlinear optical crystals; When growing potassium borosilicate nonlinear optical crystals using the high-temperature melt method, the specific operation is as follows: a. Mix the K-containing compound, the B-containing compound, and the Si-containing compound in a molar ratio of K:B:Si = 4:6:3 until homogeneous. Place the mixture in a platinum crucible and heat it in a muffle furnace to 700-900 °C. Maintain the temperature for 24-120 hours to obtain the compound K4B6Si3O. 17 The powder contains K compounds selected from KOH, K2CO3, KNO3, KHCO3, or K2SiO3; B compounds are H3BO3 or B2O3; and Si compounds are SiO2 or H2SiO3. b. The compound K4B6Si3O obtained in step a. 17 The powder and flux are mixed evenly at a molar ratio of 1:(0.1-6), and then placed in a platinum crucible. The temperature is raised to 700-900 ℃ and held for 5-120 hours to obtain a mixed melt. The flux is selected from H3BO3, B2O3, PbO or PbF2. c. Seed crystal preparation: The mixed melt obtained in step b is placed in a single crystal furnace and slowly cooled to 650 ℃ at a rate of 0.1-2 ℃ / h, then rapidly cooled to room temperature at a rate of 5-10 ℃ / h to obtain K4B6Si3O 17 Seed crystal; d. Crystal growth: The K4B6Si3O obtained in step c is grown into a crystal. 17 The seed crystal is fixed on a seed crystal rod and lowered from above the mixed melt obtained in step b. A crystal rotation of 2-20 rpm is applied using a crystal growth controller, and the temperature is lowered at a rate of 0.1-3 ℃ / h. Once crystal growth stops, K4B6Si3O is obtained. 17 Nonlinear optical crystals; When growing potassium borosilicate nonlinear optical crystals using the vacuum encapsulation method, the specific operation is as follows: a. Mix the K-containing compound, the B-containing compound, and the Si-containing compound in a molar ratio of K:B:Si = 4:6:3 until homogeneous. Place the mixture in a platinum crucible and heat it in a muffle furnace to 650-850 °C. Maintain the temperature for 24-120 hours to obtain the compound K4B6Si3O. 17 The powder contains K compounds selected from KOH, K2CO3, KNO3, KHCO3, or K2SiO3; B compounds are H3BO3 or B2O3; and Si compounds are SiO2 or H2SiO3. b. The compound K4B6Si3O obtained in step a. 17The powder and flux are mixed evenly at a molar ratio of (0.1-1):(0.1-6), placed in a quartz tube, sealed at high temperature, and then placed in a muffle furnace. The temperature is raised to 650-850 ℃ and held for 5-120 hours. Then, the temperature is lowered to 650 ℃ at a rate of 0.1-3 ℃ / h, and then rapidly cooled to room temperature at a rate of 5-10 ℃ / h to obtain K4B6Si3O. 17 Nonlinear optical crystal, wherein the flux is selected from H3BO3, B2O3, PbO or PbF2; When growing potassium borosilicate nonlinear optical crystals using the hydrothermal method, the specific operation is as follows: a. Mix the K-containing compound, the B-containing compound, and the Si-containing compound in a molar ratio of K:B:Si = 4:6:3 until homogeneous. Place the mixture in a platinum crucible and heat it in a muffle furnace to 600-850 °C. Maintain the temperature for 24-120 hours to obtain the compound K4B6Si3O. 17 The powder contains K compounds selected from KOH, K2CO3, KNO3, KHCO3, or K2SiO3; B compounds are H3BO3 or B2O3; and Si compounds are SiO2 or H2SiO3. b. The compound K4B6Si3O obtained in step a. 17 The powder was dissolved in water. The incompletely dissolved mixture was ultrasonically treated at 60 °C to ensure it was fully mixed and dissolved. The pH was adjusted to 8-11 with HF and KOH 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 the temperature to 450-600 ℃, maintain the temperature for 5-8 days, and then cool it down to room temperature at a rate of 5-20 ℃ / day to obtain K4B6Si3O. 17 Nonlinear optical crystals; When growing potassium borosilicate nonlinear optical crystals using the room temperature solution method, the specific operation is as follows: a. Mix the K-containing compound, the B-containing compound, and the Si-containing compound in a molar ratio of K:B:Si = 4:6:3 until homogeneous. Place the mixture in a platinum crucible and heat it in a muffle furnace to 700-900 °C. Maintain the temperature for 24-120 hours to obtain the compound K4B6Si3O. 17 powder; b. The compound K4B6Si3O obtained in step a. 17 Place the powder in a clean glass container, add 20-100 mL of water, and then sonicate to fully mix and dissolve. Adjust the pH to 8-11 with HF and KOH, and filter with filter paper to obtain a mixed solution. c. Place the mixed solution obtained in step b in a clean glass 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 the water in the aqueous solution. Let it stand at room temperature for 5-20 days. d. When crystal particles grow at the bottom of the container from the solution in step c, until the size of the crystal particles no longer changes significantly, seed crystals are obtained. e. Select a clean, smooth, uncontaminated, and crack-free seed crystal from step d, suspend it in the mixed solution prepared in step b, and allow it to grow at room temperature for 10-30 days to obtain K4B6Si3O. 17 Nonlinear optical crystals.

[0027] Embodiments of the present invention also provide the use of the above-described potassium borosilicate nonlinear optical crystal in the fabrication of frequency multiplier generators, up or down frequency converters, or optical parametric oscillators.

[0028] The embodiments of the present invention also provide an application of the above-mentioned potassium borosilicate nonlinear optical crystal in the preparation of second, third, fourth and fifth harmonic light output from the 1064 nm fundamental frequency light of an Nd:YAG laser.

[0029] Embodiments of the present invention also provide the use of the above-described potassium borosilicate nonlinear optical crystal in the preparation of deep ultraviolet frequency-doubled light output below 200 nm.

[0030] In the following embodiments of the present invention, the containers used include: platinum crucibles, iridium crucibles, ceramic crucibles, quartz tubes, conical flasks, beakers, and hydrothermal reactors lined with polytetrafluoroethylene or stainless steel with platinum sheaths. When the container is a quartz tube, a vacuum must be applied before sealing to prevent the quartz tube from cracking due to the volatilization of raw materials during the reaction. When the container is a conical flask or beaker, it must first be cleaned with acid, then rinsed with deionized water, and then dried.

[0031] Unless otherwise specified, the room temperature in this invention is 25±2℃.

[0032] All raw materials used in the embodiments of the present invention were obtained through commercial purchase.

[0033] It should be noted that any aspects not described in detail in this invention are conventional practices in the field and are not the focus of this invention.

[0034] The technical solution of the present invention will be further illustrated by the following embodiments.

[0035] Example 1 Preparation of compounds: According to the reaction formula: 4KOH + 6H3BO3 + 3SiO2 → K4B6Si3O17 + 11H2O, compound K4B6Si3O was synthesized by solid-state reaction. 17 : KOH, H3BO3, and SiO2 were mixed evenly in a molar ratio of 4:6:3, placed in a platinum crucible, and heated to 800 °C in a muffle furnace. The mixture was held at this temperature for 48 hours to obtain potassium borosilicate (K4B6Si3O2). 17 The powder has a molecular weight of 577.53, and its XRD pattern is shown below. Figure 1 As shown.

[0036] Example 2 Preparation of compounds: According to the reaction formula: 4KOH + 3B₂O₃ + 3SiO₂ → K₄B₆Si₃O 17 The compound K4B6Si3O was synthesized by solid-state reaction method with the addition of 2H2O. 17 : KOH, B2O3, and SiO2 were mixed evenly in a molar ratio of 4:3:3, placed in a platinum crucible, and heated to 800 °C in a muffle furnace. The mixture was held at this temperature for 48 hours to obtain the compound K4B6Si3O. 17 powder.

[0037] Example 3 Preparation of compounds: According to the reaction equation: 4KOH + 6H3BO3 + 3H2SiO3 → K4B6Si3O 17 The compound K4B6Si3O was synthesized by solid-state reaction with 14H2O. 17 : KOH, H3BO3, and H2SiO3 were mixed thoroughly in a molar ratio of 4:6:3, placed in a platinum crucible, and heated to 750 °C in a muffle furnace. The mixture was held at this temperature for 24 hours to obtain the compound K4B6Si3O. 17 powder.

[0038] Example 4 Preparation of compounds: According to the reaction equation: 4KOH + 3B₂O₃ + 3H₂SiO₃ → K₄B₆Si₃O 17 The compound K4B6Si3O was synthesized by solid-state reaction with 5H2O. 17 : KOH, B₂O₃, and H₂SiO₃ were mixed thoroughly in a molar ratio of 4:3:3, placed in a platinum crucible, and heated to 750 °C in a muffle furnace. The mixture was held at this temperature for 24 hours to obtain the compound K₄B₆Si₃O₃. 17 powder.

[0039] Example 5 Preparation of compounds: According to the reaction formula: 2K₂CO₃ + 6H₃BO₃ + 3SiO₂ → K₄B₆Si₃O 17 The compound K4B6Si3O was synthesized by solid-state reaction: ⇌ 9H2O + 2CO2. 17 : K₂CO₃, H₃BO₃, and SiO₂ were mixed thoroughly in a molar ratio of 2:6:3, placed in a platinum crucible, and heated to 800 °C in a muffle furnace. The mixture was held at this temperature for 48 hours to obtain the compound K₄B₆Si₃O. 17 powder.

[0040] Example 6 Preparation of compounds: According to the reaction formula: 2K₂CO₃ + 3B₂O₃ + 3SiO₂ → K₄B₆Si₃O 17 +2CO2, compound K4B6Si3O was synthesized by solid-state reaction method. 17 : K₂CO₃, B₂O₃, and SiO₂ were mixed evenly in a molar ratio of 2:3:3, placed in a platinum crucible, and heated to 800 °C in a muffle furnace. The mixture was held at this temperature for 48 hours to obtain the compound K₄B₆Si₃O. 17 powder.

[0041] Example 7 Preparation of compounds: According to the reaction formula: 2K₂CO₃ + 6H₃BO₃ + 3H₂SiO₃ → K₄B₆Si₃O 17 The compound K4B6Si3O was synthesized by solid-state reaction method using the reaction mixture 12H2O + 2CO2. 17 : K₂CO₃, H₃BO₃, and H₂SiO₃ were mixed thoroughly in a molar ratio of 2:6:3, placed in a platinum crucible, and heated to 750 °C in a muffle furnace. The mixture was held at this temperature for 24 hours to obtain the compound K₄B₆Si₃O₃. 17 powder.

[0042] Example 8 Preparation of compounds: According to the reaction formula: 2K₂CO₃ + 3B₂O₃ + 3H₂SiO₃ → K₄B₆Si₃O 17 The compound K4B6Si3O was synthesized by solid-state reaction method using the reaction: + 3H2O + 2CO2. 17 : K₂CO₃, B₂O₃, and H₂SiO₃ were mixed thoroughly in a molar ratio of 2:3:3, placed in a platinum crucible, and heated to 750 °C in a muffle furnace. The mixture was held at this temperature for 24 hours to obtain the compound K₄B₆Si₃O₃. 17 powder.

[0043] Example 9 Preparation of compounds: According to the reaction formula: 4KNO3 + 6H3BO3 + 3SiO2 → K4B6Si3O 17 The compound K4B6Si3O was synthesized by solid-state reaction using the reaction: + 9H2O + 4NO2 + O2. 17 : KNO3, H3BO3, and SiO2 were mixed evenly in a molar ratio of 4:6:3, placed in a platinum crucible, and heated to 800 °C in a muffle furnace. The mixture was held at this temperature for 48 hours to obtain the compound K4B6Si3O. 17 powder.

[0044] Example 10 Preparation of compounds: According to the reaction formula: 4KNO3 + 3B2O3 + 3SiO2 → K4B6Si3O 17 The compound K4B6Si3O was synthesized by solid-state reaction with 4NO2 + O2. 17 : KNO3, B2O3, and SiO2 were mixed evenly in a molar ratio of 4:3:3, placed in a platinum crucible, and heated to 800 °C in a muffle furnace. The mixture was held at this temperature for 48 hours to obtain the compound K4B6Si3O. 17 powder.

[0045] Example 11 Preparation of compounds: According to the reaction formula: 4KNO3 + 6H3BO3 + 3H2SiO3 → K4B6Si3O 17 The compound K4B6Si3O was synthesized by a solid-state reaction method involving the reaction of 12H2O with 4NO2 and O2. 17 : KNO3, H3BO3, and H2SiO3 were mixed evenly in a molar ratio of 4:6:3, placed in a platinum crucible, and heated to 750 °C in a muffle furnace. The mixture was held at this temperature for 24 hours to obtain the compound K4B6Si3O. 17 powder.

[0046] Example 12 Preparation of compounds: According to the reaction formula: 4KNO3 + 3B2O3 + 3H2SiO3 → K4B6Si3O 17 The compound K4B6Si3O was synthesized by solid-state reaction using the reaction: + 3H2O + 4NO2 + O2. 17 : KNO3, B2O3, and H2SiO3 were mixed evenly in a molar ratio of 4:3:3, placed in a platinum crucible, and heated to 750 °C in a muffle furnace. The mixture was held at this temperature for 24 hours to obtain the compound K4B6Si3O. 17 powder.

[0047] Example 13 Preparation of compounds: According to the reaction formula: 4KHCO3 + 6H3BO3 + 3SiO2 → K4B6Si3O 17 The compound K4B6Si3O was synthesized by solid-state reaction using the reaction 11H2O + 4CO2. 17 : KHCO3, H3BO3, and SiO2 were mixed evenly in a molar ratio of 4:6:3, placed in a platinum crucible, and heated to 800 °C in a muffle furnace. The mixture was held at this temperature for 48 hours to obtain the compound K4B6Si3O. 17 powder.

[0048] Example 14 Preparation of compounds: According to the reaction formula: 4KHCO3 + 3B2O3 + 3SiO2 → K4B6Si3O 17 The compound K4B6Si3O was synthesized by solid-state reaction 2H2O + 4CO2. 17 : KHCO3, B2O3, and SiO2 were mixed evenly in a molar ratio of 4:3:3, placed in a platinum crucible, and heated to 800 °C in a muffle furnace. The mixture was held at this temperature for 48 hours to obtain the compound K4B6Si3O. 17 powder.

[0049] Example 15 Preparation of compounds: According to the reaction formula: 4KHCO3 + 6H3BO3 + 3H2SiO3 → K4B6Si3O 17 The compound K4B6Si3O was synthesized by solid-state reaction using the reaction 14H2O + 4CO2. 17 : KHCO3, H3BO3, and H2SiO3 were mixed evenly in a molar ratio of 4:6:3, placed in a platinum crucible, and heated to 750 °C in a muffle furnace. The mixture was held at this temperature for 24 hours to obtain the compound K4B6Si3O. 17 powder.

[0050] Example 16 Preparation of compounds: According to the reaction formula: 4KHCO3 + 3B2O3 + 3H2SiO3 → K4B6Si3O 17The compound K4B6Si3O was synthesized by solid-state reaction of 5H2O + 4CO2. 17 : KHCO3, B2O3, and H2SiO3 were mixed evenly in a molar ratio of 4:3:3, placed in a platinum crucible, and heated to 750 °C in a muffle furnace. The mixture was held at this temperature for 24 hours to obtain the compound K4B6Si3O. 17 powder.

[0051] Example 17 Preparation of compounds: According to the reaction formula: 2K₂SiO₃ + 6H₃BO₃ + SiO₂ → K₄B₆Si₃O 17 + 9H2O, compound K4B6Si3O was synthesized by solid-state reaction. 17 : K2SiO3, H3BO3, and SiO2 were mixed evenly in a molar ratio of 2:6:1, placed in a platinum crucible, and heated to 800 °C in a muffle furnace. The mixture was held at this temperature for 48 hours to obtain the compound K4B6Si3O. 17 powder.

[0052] Example 18 Preparation of compounds: According to the reaction formula: 2K₂SiO₃ + 3B₂O₃ + SiO₂ → K₄B₆Si₃O 17 Compound K4B6Si3O was synthesized using a solid-state reaction method. 17 : K₂SiO₃, B₂O₃, and SiO₂ were mixed evenly in a molar ratio of 2:3:1, placed in a platinum crucible, and heated to 800 °C in a muffle furnace. The mixture was held at this temperature for 48 hours to obtain the compound K₄B₆Si₃O. 17 powder.

[0053] Example 19 Preparation of compounds: According to the reaction formula: 2K₂SiO₃ + 6H₃BO₃ + H₂SiO₃ → K₄B₆Si₃O 17 The compound K4B6Si3O was synthesized by solid-state reaction with 10H2O. 17 : K₂SiO₃, H₃BO₃, and H₂SiO₃ were mixed evenly in a molar ratio of 2:6:1, placed in a platinum crucible, and heated to 750 °C in a muffle furnace. The mixture was held at this temperature for 24 hours to obtain the compound K₄B₆Si₃O₃. 17 powder.

[0054] Example 20 Preparation of compounds: According to the reaction formula: 2K₂SiO₃ + 3B₂O₃ + H₂SiO₃ → K₄B₆Si₃O 17 + H2O, compound K4B6Si3O was synthesized by solid-state reaction method. 17 : K₂SiO₃, B₂O₃, and H₂SiO₃ were mixed evenly in a molar ratio of 2:3:1, placed in a platinum crucible, and heated to 750 °C in a muffle furnace. The mixture was held at this temperature for 24 hours to obtain the compound K₄B₆Si₃O. 17 powder.

[0055] Example 21 Preparation of compounds: According to the reaction formula: 4KOH + 6H3BO3 + 3SiO2 → K4B6Si3O 17 + 11H2O, compound K4B6Si3O was synthesized by vacuum encapsulation. 17 : KOH, H3BO3, and SiO2 were mixed evenly in a molar ratio of 4:6:3 and then placed into a Φ40 mm quartz tube. The quartz tube was then evacuated to a vacuum level of 1×10⁻⁶. -3 Pa, after being sealed at high temperature, was placed in a muffle furnace and heated to 580℃ at a rate of 5℃ / h, and held at that temperature for 96 hours to obtain compound K4B6Si3O. 17 powder.

[0056] Example 22 Preparation of compounds: According to the reaction formula: 4KOH + 3B₂O₃ + 3SiO₂ → K₄B₆Si₃O 17 +2H₂O, compound K₄B₆Si₃O was synthesized by vacuum encapsulation. 17 : KOH, B2O3, and SiO2 were mixed evenly in a molar ratio of 4:3:3 and then placed into a Φ40 mm quartz tube. The quartz tube was then evacuated to a vacuum level of 1×10⁻⁶. -3 Pa, after being sealed at high temperature, was placed in a muffle furnace and heated to 680℃ at a rate of 5℃ / h, and held at that temperature for 96 hours to obtain compound K4B6Si3O. 17 powder.

[0057] Example 23 Preparation of compounds: According to the reaction equation: 4KOH + 6H3BO3 + 3H2SiO3 → K4B6Si3O 17 + 14H2O, compound K4B6Si3O was synthesized by vacuum encapsulation. 17 : KOH, H3BO3, and H2SiO3 were mixed evenly in a molar ratio of 4:6:3 and then placed into a Φ40 mm quartz tube. The quartz tube was then evacuated to a vacuum level of 1×10⁻⁶. -3 Pa, after being sealed at high temperature, was placed in a muffle furnace and heated to 680 °C at a rate of 5 °C / h, and held at that temperature for 96 hours to obtain compound K4B6Si3O. 17 powder.

[0058] Example 24 Preparation of compounds: According to the reaction equation: 4KOH + 3B₂O₃ + 3H₂SiO₃ → K₄B₆Si₃O 17 + 5H2O, compound K4B6Si3O was synthesized by vacuum encapsulation. 17 : KOH, B2O3, and H2SiO3 were mixed evenly in a molar ratio of 4:3:3 and then placed into a Φ40 mm quartz tube. The quartz tube was then evacuated to a vacuum level of 1×10⁻⁶. -3 Pa, after being sealed at high temperature, was placed in a muffle furnace and heated to 680℃ at a rate of 5℃ / h, and held at that temperature for 96 hours to obtain compound K4B6Si3O. 17 powder.

[0059] Example 25 Preparation of compounds: According to the reaction formula: 2K₂CO₃ + 6H₃BO₃ + 3SiO₂ → K₄B₆Si₃O 17 The compound K4B6Si3O was synthesized using a vacuum encapsulation method, consisting of 9H2O and 2CO2. 17 : K₂CO₃, H₃BO₃, and SiO₂ were mixed evenly in a molar ratio of 2:6:3 and then placed into a Φ40 mm quartz tube. The quartz tube was then evacuated to a vacuum level of 1×10⁻⁶. -3 Pa, after being sealed at high temperature, was placed in a muffle furnace and heated to 680℃ at a rate of 5℃ / h, and held at that temperature for 96 hours to obtain compound K4B6Si3O. 17 powder.

[0060] Example 26 Preparation of compounds: According to the reaction formula: 2K₂CO₃ + 3B₂O₃ + 3SiO₂ → K₄B₆Si₃O 17 +2CO2, compound K4B6Si3O was synthesized using a vacuum encapsulation method. 17 : K₂CO₃, B₂O₃, and SiO₂ were mixed evenly in a molar ratio of 2:3:3 and then placed into a Φ40 mm quartz tube. The quartz tube was then evacuated to a vacuum level of 1×10⁻⁶.-3 Pa, after being sealed at high temperature, was placed in a muffle furnace and heated to 680℃ at a rate of 5℃ / h, and held at that temperature for 96 hours to obtain compound K4B6Si3O. 17 powder.

[0061] Example 27 Preparation of compounds: According to the reaction formula: 2K₂CO₃ + 6H₃BO₃ + 3H₂SiO₃ → K₄B₆Si₃O 17 The compound K4B6Si3O was synthesized using a vacuum encapsulation method after the reaction of 12H2O and 2CO2. 17 : K₂CO₃, H₃BO₃, and H₂SiO₃ were mixed evenly in a molar ratio of 2:6:3 and then placed into a Φ40 mm quartz tube. The quartz tube was then evacuated to a vacuum level of 1×10⁻⁶. -3 Pa, after being sealed at high temperature, was placed in a muffle furnace and heated to 680 °C at a rate of 5 °C / h, and held at that temperature for 96 hours to obtain compound K4B6Si3O. 17 powder.

[0062] Example 28 Preparation of compounds: According to the reaction formula: 2K₂CO₃ + 3B₂O₃ + 3H₂SiO₃ → K₄B₆Si₃O 17 The compound K4B6Si3O was synthesized using a vacuum encapsulation method after the reaction of 3H2O and 2CO2. 17 : K₂CO₃, B₂O₃, and H₂SiO₃ were mixed evenly in a molar ratio of 2:3:3 and then placed into a Φ40 mm quartz tube. The quartz tube was then evacuated to a vacuum level of 1×10⁻⁶. -3 Pa, after being sealed at high temperature, was placed in a muffle furnace and heated to 680 °C at a rate of 5 °C / h, and held at that temperature for 96 hours to obtain compound K4B6Si3O. 17 powder.

[0063] Example 29 Preparation of compounds: According to the reaction formula: 4KNO3 + 6H3BO3 + 3SiO2 → K4B6Si3O 17 The compound K4B6Si3O was synthesized using a vacuum encapsulation method, consisting of 9H2O, 4NO2, and O2. 17 : KNO3, H3BO3, and SiO2 were mixed evenly in a molar ratio of 4:6:3 and then placed into a Φ40 mm quartz tube. The quartz tube was then evacuated to a vacuum level of 1×10⁻⁶. -3Pa, after being sealed at high temperature, was placed in a muffle furnace and heated to 600℃ at a rate of 5℃ / h, and held at that temperature for 96 hours to obtain the compound K4B6Si3O. 17 powder.

[0064] Example 30 Preparation of compounds: According to the reaction formula: 4KNO3 + 3B2O3 + 3SiO2 → K4B6Si3O 17 + 4NO2+ O2, compound K4B6Si3O was synthesized using a vacuum encapsulation method. 17 : KNO3, B2O3, and SiO2 were mixed evenly in a molar ratio of 4:3:3 and then placed into a Φ40 mm quartz tube. The quartz tube was then evacuated to a vacuum level of 1×10⁻⁶. -3 Pa, after being sealed at high temperature, was placed in a muffle furnace and heated to 600℃ at a rate of 5℃ / h, and held at that temperature for 96 hours to obtain the compound K4B6Si3O. 17 powder.

[0065] Example 31 Preparation of compounds: According to the reaction formula: 4KNO3 + 6H3BO3 + 3H2SiO3 → K4B6Si3O 17 The compound K4B6Si3O was synthesized using a vacuum encapsulation method, consisting of 12H2O + 4NO2 + O2. 17 : KNO3, H3BO3, and H2SiO3 were mixed evenly in a molar ratio of 4:6:3 and then placed into a Φ40 mm quartz tube. The quartz tube was then evacuated to a vacuum level of 1×10⁻⁶. -3 Pa, after being sealed at high temperature, was placed in a muffle furnace and heated to 600 °C at a rate of 5 °C / h, and held at that temperature for 96 hours to obtain the compound K4B6Si3O. 17 powder.

[0066] Example 32 Preparation of compounds: According to the reaction formula: 4KNO3 + 3B2O3 + 3H2SiO3 → K4B6Si3O 17 The compound K4B6Si3O was synthesized using a vacuum encapsulation method, consisting of 3H2O + 4NO2 + O2. 17 : KNO3, B2O3, and H2SiO3 were mixed evenly in a molar ratio of 4:3:3 and then placed into a Φ40 mm quartz tube. The quartz tube was then evacuated to a vacuum level of 1×10⁻⁶. -3Pa, after being sealed at high temperature, was placed in a muffle furnace and heated to 600℃ at a rate of 5℃ / h, and held at that temperature for 96 hours to obtain the compound K4B6Si3O. 17 powder.

[0067] Example 33 Preparation of compounds: According to the reaction formula: 4KHCO3 + 6H3BO3 + 3SiO2 → K4B6Si3O 17 The compound K4B6Si3O was synthesized using a vacuum encapsulation method, consisting of 11H2O and 4CO2. 17 : KHCO3, H3BO3, and SiO2 were mixed evenly in a molar ratio of 4:6:3 and then placed into a Φ40 mm quartz tube. The quartz tube was then evacuated to a vacuum level of 1×10⁻⁶. -3 Pa, after being sealed at high temperature, was placed in a muffle furnace and heated to 580 °C at a rate of 5 °C / h, and held at that temperature for 96 hours to obtain compound K4B6Si3O. 17 powder.

[0068] Example 34 Preparation of compounds: According to the reaction formula: 4KHCO3 + 3B2O3 + 3SiO2 → K4B6Si3O 17 The compound K4B6Si3O was synthesized using a vacuum encapsulation method, consisting of 2H2O and 4CO2. 17 : KHCO3, B2O3, and SiO2 were mixed evenly in a molar ratio of 4:3:3 and then placed into a Φ40 mm quartz tube. The quartz tube was then evacuated to a vacuum level of 1×10⁻⁶. -3 Pa, after being sealed at high temperature, was placed in a muffle furnace and heated to 580℃ at a rate of 5℃ / h, and held at that temperature for 96 hours to obtain compound K4B6Si3O. 17 powder.

[0069] Example 35 Preparation of compounds: According to the reaction formula: 4KHCO3 + 6H3BO3 + 3H2SiO3 → K4B6Si3O 17 The compound K4B6Si3O was synthesized using a vacuum encapsulation method, consisting of 14H2O and 4CO2. 17 : KHCO3, H3BO3, and H2SiO3 were mixed evenly in a molar ratio of 4:6:3 and then placed into a Φ40 mm quartz tube. The quartz tube was then evacuated to a vacuum level of 1×10⁻⁶. -3Pa, after being sealed at high temperature, was placed in a muffle furnace and heated to 580 °C at a rate of 5 °C / h, and held at that temperature for 96 hours to obtain compound K4B6Si3O. 17 powder.

[0070] Example 36 Preparation of compounds: According to the reaction formula: 4KHCO3 + 3B2O3 + 3H2SiO3 → K4B6Si3O 17 The compound K4B6Si3O was synthesized using a vacuum encapsulation method, consisting of 5H2O and 4CO2. 17 : KHCO3, B2O3, and H2SiO3 were mixed evenly in a molar ratio of 4:3:3 and then placed into a Φ40 mm quartz tube. The quartz tube was then evacuated to a vacuum level of 1×10⁻⁶. -3 Pa, after being sealed at high temperature, was placed in a muffle furnace and heated to 580 °C at a rate of 5 °C / h, and held at that temperature for 96 hours to obtain compound K4B6Si3O. 17 powder.

[0071] Example 37 Preparation of compounds: According to the reaction formula: 2K₂SiO₃ + 6H₃BO₃ + SiO₂ → K₄B₆Si₃O 17 + 9H2O, compound K4B6Si3O was synthesized by vacuum encapsulation. 17 : K2SiO3, H3BO3, and SiO2 were mixed evenly in a molar ratio of 2:6:1 and then placed into a Φ40 mm quartz tube. The quartz tube was then evacuated to a vacuum level of 1×10⁻⁶. -3 Pa, after being sealed at high temperature, was placed in a muffle furnace and heated to 660 °C at a rate of 5 °C / h, and held at that temperature for 96 hours to obtain the compound K4B6Si3O. 17 powder.

[0072] Example 38 Preparation of compounds: According to the reaction formula: 2K₂SiO₃ + 3B₂O₃ + SiO₂ → K₄B₆Si₃O 17 The compound K4B6Si3O was synthesized using a vacuum encapsulation method. 17 : K₂SiO₃, B₂O₃, and SiO₂ were mixed evenly in a molar ratio of 2:3:1 and then placed into a Φ40 mm quartz tube. The quartz tube was then evacuated to a vacuum level of 1×10⁻⁶. -3 Pa, after being sealed at high temperature, was placed in a muffle furnace and heated to 580℃ at a rate of 5℃ / h, and held at that temperature for 96 hours to obtain compound K4B6Si3O.17 powder.

[0073] Example 39 Preparation of compounds: According to the reaction formula: 2K₂SiO₃ + 6H₃BO₃ + H₂SiO₃ → K₄B₆Si₃O 17 + 10H2O, compound K4B6Si3O was synthesized by vacuum encapsulation. 17 : K₂SiO₃, H₃BO₃, and H₂SiO₃ were mixed evenly in a molar ratio of 2:6:1 and then placed into a Φ40 mm quartz tube. The quartz tube was then evacuated to a vacuum level of 1×10⁻⁶. -3 Pa, after being sealed at high temperature, was placed in a muffle furnace and heated to 660 °C at a rate of 5 °C / h, and held at that temperature for 96 hours to obtain the compound K4B6Si3O. 17 powder.

[0074] Example 40 Preparation of compounds: According to the reaction formula: 2K₂SiO₃ + 3B₂O₃ + H₂SiO₃ → K₄B₆Si₃O 17 + H2O, compound K4B6Si3O was synthesized using a vacuum encapsulation method. 17 : K₂SiO₃, B₂O₃, and H₂SiO₃ were mixed evenly in a molar ratio of 2:3:1 and then placed into a Φ40 mm quartz tube. The quartz tube was then evacuated to a vacuum level of 1×10⁻⁶. -3 Pa, after being sealed at high temperature, was placed in a muffle furnace and heated to 660 °C at a rate of 5 °C / h, and held at that temperature for 96 hours to obtain the compound K4B6Si3O. 17 powder.

[0075] Example 41 Preparation of compounds: According to the reaction formula: 4KOH + 6H3BO3 + 3SiO2 → K4B6Si3O 17 + 11H2O, compound K4B6Si3O was synthesized by solid-state reaction. 17 : KOH, H3BO3, and SiO2 were mixed evenly in a molar ratio of 4:6:3, and the mixture was placed in an autoclave and heated to 550 °C in a muffle furnace. The mixture was held at this temperature for 48 hours to obtain the compound K4B6Si3O. 17 powder.

[0076] Example 42 Preparation of compounds: According to the reaction formula: 4KOH + 3B₂O₃ + 3SiO₂ → K₄B₆Si₃O17 The compound K4B6Si3O was synthesized by solid-state reaction method with the addition of 2H2O. 17 : KOH, B2O3, and SiO2 were mixed evenly in a molar ratio of 4:3:3, and the mixture was placed in an autoclave and heated to 550 °C in a muffle furnace. The mixture was held at this temperature for 48 hours to obtain the compound K4B6Si3O. 17 powder.

[0077] Example 43 Preparation of compounds: According to the reaction equation: 4KOH + 6H3BO3 + 3H2SiO3 → K4B6Si3O 17 The compound K4B6Si3O was synthesized by solid-state reaction with 14H2O. 17 : KOH, H3BO3, and H2SiO3 were mixed evenly in a molar ratio of 4:6:3, and the mixture was placed in an autoclave and heated to 550 °C in a muffle furnace. The mixture was held at this temperature for 48 hours to obtain the compound K4B6Si3O. 17 powder.

[0078] Example 44 Preparation of compounds: According to the reaction equation: 4KOH + 3B₂O₃ + 3H₂SiO₃ → K₄B₆Si₃O 17 The compound K4B6Si3O was synthesized by solid-state reaction with 5H2O. 17 : KOH, B2O3, and H2SiO3 were mixed evenly in a molar ratio of 4:3:3, and the mixture was placed in an autoclave and heated to 550 °C in a muffle furnace. The mixture was held at this temperature for 48 hours to obtain the compound K4B6Si3O. 17 powder.

[0079] Example 45 Melt growth of K4B6Si3O 17 Nonlinear optical crystals: The compound K4B6Si3O prepared in Example 1 17 The powder was placed in a platinum crucible, placed in a muffle furnace, heated to 750°C, and held at that temperature for 10 hours to obtain a mixed melt. The resulting mixed melt was slowly cooled to 650 °C at a rate of 0.1 °C / h, and then rapidly cooled to room temperature at a rate of 5 °C / h to obtain K4B6Si3O. 17 Seed crystal; Crystals were grown using the Czochralski method: the obtained K4B6Si3O 17The seed crystal is fixed on a seed crystal rod and lowered from above the prepared mixed melt. A crystal rotation of 2 rpm is applied using a crystal growth controller, and the seed crystal is pulled up at a rate of 1 mm / day. The temperature is lowered at a rate of 0.1 ℃ / h. After crystal growth stops, potassium borosilicate (K4B6Si3O4) with dimensions of 10 mm × 12 mm × 9 mm is obtained. 17 Nonlinear optical crystal, structure diagram as follows Figure 2 As shown, the molecular weight is 577.53, it belongs to the monoclinic crystal system, and its space group is [space group number missing]. C 2. The unit cell parameters are a = 11.8628(13) Å, b = 6.6285(6) Å, c = 11.0097(19) Å, β =117.183(4)°, unit cell volume is 770.10(17) Å 3 .

[0080] Example 46 Melt growth of K4B6Si3O 17 Nonlinear optical crystals: The compound K4B6Si3O prepared in Example 3 17 The powder was placed in a platinum crucible, placed in a muffle furnace, heated to 750°C, and held at that temperature for 120 hours to obtain a mixed melt. The resulting mixed melt was slowly cooled to 650 °C at a rate of 2 °C / h, and then rapidly cooled to room temperature at a rate of 10 °C / h to obtain K4B6Si3O. 17 Seed crystal; Crystals were grown using the Czochralski method: the obtained K4B6Si3O 17 The seed crystal is fixed on a seed crystal rod and lowered from above the prepared mixed melt. A crystal rotation of 20 rpm is applied using a crystal growth controller, and the seed crystal is pulled up at a rate of 10 mm / day. The temperature is then reduced at a rate of 10 ℃ / h. Once crystal growth stops, a K4B6Si3O crystal with dimensions of 12 mm × 10 mm × 8 mm is obtained. 17 Nonlinear optical crystals.

[0081] Example 47 Melt growth of K4B6Si3O 17 Nonlinear optical crystals: The compound K4B6Si3O prepared in Example 2 17 The powder was placed in a platinum crucible, placed in a muffle furnace, heated to 700°C, and held at that temperature for 100 hours to obtain a mixed melt. The resulting mixed melt was slowly cooled to 650 °C at a rate of 1.5 °C / h, and then rapidly cooled to room temperature at a rate of 8 °C / h to obtain K4B6Si3O. 17 Seed crystal; Crystals were grown using the Czochralski method: the obtained K4B6Si3O 17 The seed crystal is fixed on a seed crystal rod and lowered from above the prepared mixed melt. The temperature is lowered at a rate of 0.1 ℃ / h to allow the crystal to grow for 5 hours. The crystal is then slowly raised without leaving the liquid surface and growth continues. This process is repeated three times to obtain a K4B6Si3O crystal with dimensions of 11 mm × 10 mm × 9 mm. 17 Nonlinear optical crystals.

[0082] Example 48 Melt growth of K4B6Si3O 17 Nonlinear optical crystals: The compound K4B6Si3O prepared in Example 4 17 The powder was placed in a platinum crucible, placed in a muffle furnace, heated to 700°C, and held at that temperature for 24 hours to obtain a mixed melt. The resulting mixed melt was slowly cooled to 650 °C at a rate of 1 °C / h, and then rapidly cooled to room temperature at a rate of 6 °C / h to obtain K4B6Si3O. 17 Seed crystal; Crystals were grown using the Czochralski method: the obtained K4B6Si3O 17 The seed crystal is fixed on a seed crystal rod and lowered from above the prepared mixed melt. The temperature is lowered at a rate of 10 °C / h to allow the crystal to grow for 15 hours. The crystal is then slowly raised without leaving the liquid surface to continue growth. This process is repeated three times to obtain a K4B6Si3O crystal with dimensions of 15 mm × 13 mm × 10 mm. 17 Nonlinear optical crystals.

[0083] Example 49 Melt growth of K4B6Si3O 17 Nonlinear optical crystals: The compound K4B6Si3O prepared in Example 5 17 The powder was placed in a platinum crucible, heated to 700 °C, and held at that temperature for 10 hours to obtain a mixed melt. The resulting mixed melt was slowly cooled to 650 °C at a rate of 2 °C / h, and then rapidly cooled to room temperature at a rate of 5 °C / h to obtain K4B6Si3O. 17 Seed crystal; Crystal growth in compound melt using the crucible lowering method: The obtained K4B6Si3O 17The seed crystal was placed at the bottom of the crucible, and then the compound K4B6Si3O prepared in Example 5 was added. 17 The powder was placed in a crucible, which was then sealed. The growth furnace temperature was raised to 750 °C and held for 10 hours. The crucible position was adjusted to allow the seed crystal to partially melt. The crucible was then lowered at a rate of 1 mm / day, and the temperature was reduced to 550 °C at a rate of 3 °C / h. After growth was completed, the temperature was rapidly reduced to room temperature at a rate of 10 °C / h, resulting in a K4B6Si3O crystal with dimensions of 13 mm × 11 mm × 10 mm. 17 Nonlinear optical crystals.

[0084] Example 50 Melt growth of K4B6Si3O 17 Nonlinear optical crystals: The compound K4B6Si3O prepared in Example 6 17 The powder was placed in a platinum crucible, heated to 730 °C, and held at that temperature for 60 hours to obtain a mixed melt. The resulting mixed melt was slowly cooled to 650 °C at a rate of 1.5 °C / h, and then rapidly cooled to room temperature at a rate of 5 °C / h to obtain K4B6Si3O. 17 Seed crystal; Crystal growth in compound melt using the crucible lowering method: The obtained K4B6Si3O 17 The seed crystal is placed at the bottom of the crucible, and then the compound K4B6Si3O prepared in Example 6 is added. 17 The powder was placed in a crucible, which was then sealed. The growth furnace temperature was raised to 650 °C and held constant for 120 hours. The crucible position was adjusted to allow the seed crystal to partially melt. The crucible was then lowered at a rate of 10 mm / day while maintaining the growth temperature. After growth was complete, the temperature was rapidly reduced to room temperature at a rate of 10 °C / h, resulting in a K4B6Si3O crystal with dimensions of 11 mm × 10 mm × 9 mm. 17 Nonlinear optical crystals.

[0085] Example 51 High-temperature melt growth of K4B6Si3O 17 Nonlinear optical crystals: The compound K4B6Si3O prepared in Example 8 17 The powder and flux B2O3 were mixed evenly at a molar ratio of 1:0.1, placed in a platinum crucible, heated to 750 °C, and kept at the temperature for 5 hours to obtain a mixed melt. Seed crystal preparation: The obtained mixed melt was placed in a single crystal furnace and slowly cooled to 650℃ at a rate of 0.1℃ / h, and then rapidly cooled to room temperature at a rate of 5℃ / h to obtain K4B6Si3O. 17Seed crystal; Crystal growth: The obtained K4B6Si3O 17 The seed crystal is fixed on a seed crystal rod and lowered from above the prepared mixed melt. A crystal rotation of 2 rpm is applied using a crystal growth controller, and the temperature is lowered at a rate of 0.1 ℃ / h. After crystal growth stops, a K4B6Si3O crystal with dimensions of 12 mm × 10 mm × 8 mm is obtained. 17 Nonlinear optical crystals.

[0086] Example 52 High-temperature melt growth of K4B6Si3O 17 Nonlinear optical crystals: The compound K4B6Si3O prepared in Example 9 17 The powder and flux H3BO3 were mixed evenly at a molar ratio of 1:6, and then placed in a platinum crucible. The temperature was raised to 730 °C and held for 52 hours to obtain a mixed melt. Seed crystal preparation: The obtained mixed melt was placed in a single crystal furnace and slowly cooled to 650℃ at a rate of 1℃ / h, and then rapidly cooled to room temperature at a rate of 8℃ / h to obtain K4B6Si3O. 17 Seed crystal; Crystal growth: The obtained K4B6Si3O 17 The seed crystal is fixed on a seed crystal rod and lowered from above the prepared mixed molten crystal. A crystal rotation of 10 rpm is applied using a crystal growth controller, and the temperature is lowered at a rate of 1 °C / h. After crystal growth stops, a K4B6Si3O crystal with dimensions of 12 mm × 11 mm × 10 mm is obtained. 17 Nonlinear optical crystals.

[0087] Example 53 High-temperature melt growth of K4B6Si3O 17 Nonlinear optical crystals: The compound K4B6Si3O prepared in Example 10 17 The powder and flux PbO were mixed evenly at a molar ratio of 1:4, placed in a platinum crucible, heated to 600 °C, and kept at the temperature for 5 hours to obtain a mixed melt. Seed crystal preparation: The obtained mixed melt was placed in a single crystal furnace and slowly cooled to 550℃ at a rate of 1.5℃ / h, and then rapidly cooled to room temperature at a rate of 10℃ / h to obtain K4B6Si3O 17 Seed crystal; Crystal growth: The obtained K4B6Si3O 17The seed crystal is fixed on a seed crystal rod and lowered from above the prepared mixed molten crystal. A crystal rotation of 10 rpm is applied using a crystal growth controller, and the temperature is lowered at a rate of 1 °C / h. After crystal growth stops, a K4B6Si3O crystal with dimensions of 11 mm × 11 mm × 10 mm is obtained. 17 Nonlinear optical crystals.

[0088] Example 54 High-temperature melt growth of K4B6Si3O 17 Nonlinear optical crystals: The compound K4B6Si3O prepared in Example 11 17 The powder and flux PbF2 were mixed evenly at a molar ratio of 1:3, then placed in a platinum crucible, heated to 600 °C, and held at that temperature for 120 hours to obtain a mixed melt. Seed crystal preparation: The obtained mixed melt was placed in a single crystal furnace and slowly cooled to 550℃ at a rate of 2℃ / h, and then rapidly cooled to room temperature at a rate of 10℃ / h to obtain K4B6Si3O 17 Seed crystal; Crystal growth: The obtained K4B6Si3O 17 The seed crystal is fixed on a seed crystal rod and lowered from above the prepared mixed melt. A crystal rotation of 15 rpm is applied using a crystal growth controller, and the temperature is lowered at a rate of 0.2 ℃ / h. After crystal growth stops, a K4B6Si3O crystal with dimensions of 14 mm × 12 mm × 11 mm is obtained. 17 Nonlinear optical crystals.

[0089] Example 55 K4B6Si3O grown by vacuum encapsulation method 17 Nonlinear optical crystals: The compound K4B6Si3O prepared in Example 11 17 The powder and flux H3BO3 were mixed evenly at a molar ratio of 1:4, and then packed into a Φ40 mm quartz tube. The quartz tube was then evacuated to a vacuum level of 1×10⁻⁶. -3 Pa, after being sealed at high temperature, was placed in a muffle furnace and heated to 650 °C, held at that temperature for 5 hours, then cooled to 550 °C at a rate of 0.1 °C / h, and then rapidly cooled to room temperature at a rate of 8 °C / h, thus obtaining K4B6Si3O with dimensions of 4 mm × 3 mm × 2 mm. 17 Nonlinear optical crystals.

[0090] Example 56 K4B6Si3O grown by vacuum encapsulation method 17 Nonlinear optical crystals: The compound K4B6Si3O prepared according to Example 1 was... 17 The powder and flux H3BO3 were mixed evenly at a molar ratio of 1:6, and then packed into a Φ40 mm quartz tube. The quartz tube was then evacuated to a vacuum level of 1×10⁻⁶. -3 Pa, after being sealed at high temperature, was placed in a muffle furnace and heated to 750 °C, held at that temperature for 50 hours, then cooled to 650 °C at a rate of 2 °C / h, and then rapidly cooled to room temperature at a rate of 10 °C / h, thus obtaining K4B6Si3O with dimensions of 4 mm × 2 mm × 2 mm. 17 Nonlinear optical crystals.

[0091] Example 57 K4B6Si3O grown by vacuum encapsulation method 17 Nonlinear optical crystals: The compound K4B6Si3O prepared in Example 1 17 The powder and flux B2O3 were mixed evenly at a molar ratio of 1:1, and then packed into a Φ40 mm quartz tube. The quartz tube was then evacuated to a vacuum level of 1×10⁻⁶. -3 Pa, after being sealed at high temperature, was placed in a muffle furnace and heated to 750 °C, held at that temperature for 120 hours, then cooled to 650 °C at a rate of 1 °C / h, and then rapidly cooled to room temperature at a rate of 8 °C / h, thus obtaining K4B6Si3O with dimensions of 5 mm × 3 mm × 3 mm. 17 Nonlinear optical crystals.

[0092] Example 58 K4B6Si3O grown by vacuum encapsulation method 17 Nonlinear optical crystals: The compound K4B6Si3O prepared in Example 1 17 The powder and flux PbO were mixed evenly at a molar ratio of 1:2, and then packed into a Φ40 mm quartz tube. The quartz tube was then evacuated to a vacuum level of 1×10⁻⁶. -3 Pa, after being sealed at high temperature, was placed in a muffle furnace and heated to 700 °C, held at that temperature for 48 hours, then cooled to 650 °C at a rate of 1.5 °C / h, and then rapidly cooled to room temperature at a rate of 5 °C / h, thus obtaining K4B6Si3O with dimensions of 4 mm × 3 mm × 3 mm. 17 Nonlinear optical crystals.

[0093] Example 59 K4B6Si3O grown by vacuum encapsulation method 17 Nonlinear optical crystals: The compound K4B6Si3O prepared in Example 1 17The powder and flux PbF2 were mixed evenly at a molar ratio of 1:4, and then packed into a Φ40 mm quartz tube. The quartz tube was then evacuated to a vacuum level of 1×10⁻⁶. -3 Pa, after being sealed at high temperature, was placed in a muffle furnace and heated to 750 °C, held at that temperature for 96 hours, then cooled to 550 °C at a rate of 0.2 °C / h, and then rapidly cooled to room temperature at a rate of 5 °C / h, thus obtaining K4B6Si3O with dimensions of 5 mm × 4 mm × 3 mm. 17 Nonlinear optical crystals.

[0094] Example 60 Hydrothermal growth of potassium borosilicate nonlinear optical crystals: The compound K4B6Si3O prepared in Example 4 17 The powder was dissolved in deionized water. The incompletely dissolved mixture was ultrasonically treated at 60 °C to ensure thorough mixing and dissolution. The pH was adjusted to 8 using HF and KOH. The resulting mixed solution was transferred into the liner of a clean, uncontaminated 100 mL high-pressure reactor, and the reactor was then tightly sealed. The high-pressure reactor was placed in a constant temperature chamber, heated to 500 °C, and held at that temperature for 8 days. Then, it was cooled to room temperature at a rate of 5 °C / day; this yielded K4B6Si3O with dimensions of 3 mm × 3 mm × 2 mm. 17 Nonlinear optical crystals.

[0095] Example 61 Hydrothermal growth of potassium borosilicate nonlinear optical crystals: The compound K4B6Si3O prepared in Example 8 17 The powder was dissolved in deionized water. The incompletely dissolved mixture was ultrasonically treated at 60 °C to ensure thorough mixing and dissolution. The pH was adjusted to 11 using HF and KOH. The resulting mixed solution was transferred into the liner of a clean, uncontaminated 100 mL high-pressure reactor, and the reactor was then tightly sealed. The high-pressure reactor was placed in a constant temperature chamber, heated to 550 °C, and held at that temperature for 5 days. Then, it was cooled to room temperature at a rate of 20 °C / day; this yielded K4B6Si3O with dimensions of 4 mm × 3 mm × 3 mm. 17 Nonlinear optical crystals.

[0096] Example 62 Potassium borosilicate nonlinear optical crystals grown by room temperature solution method The compound K4B6Si3O prepared in Example 9 17Place the powder into a clean glass container, add 20 mL of deionized water, and then sonicate to mix and dissolve thoroughly. Adjust the pH of the solution to 8 with HF and KOH, and filter with filter paper to obtain a mixed solution. Place the obtained mixed solution in a clean Erlenmeyer flask, 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 the water in the aqueous solution, and let it stand at room temperature for 5 days. Seed crystals are obtained when crystal particles grow at the bottom of the container and their size no longer changes significantly. Select a clean, flat, uncontaminated, and crack-free seed crystal, suspend it in the prepared mixed solution, and allow it to grow at room temperature for 30 days to obtain a K4B6Si3O crystal with dimensions of 11 mm × 7 mm × 7 mm. 17 Nonlinear optical crystals.

[0097] Example 63 Potassium borosilicate nonlinear optical crystals grown by room temperature solution method The compound K4B6Si3O prepared in Example 10 17 Place the powder into a clean glass container, add 100 mL of deionized water, and then sonicate to mix and dissolve thoroughly. Adjust the pH of the solution to 11 with HF and KOH, and filter the solution with filter paper to obtain the solution. b. Place the obtained solution in a clean Erlenmeyer flask, 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 the water in the aqueous solution. Let it stand at room temperature for 5 days. Seed crystals are obtained when crystal particles grow at the bottom of the container and their size no longer changes significantly. Select a seed crystal with a clean, flat, uncontaminated, and crack-free surface, suspend it in the prepared mixed solution, and allow it to grow at room temperature for 10 days to obtain a potassium borosilicate nonlinear optical crystal with a size of 4 mm × 3 mm × 3 mm.

[0098] Example 64 The arbitrary K4B6Si3O obtained in Examples 45-63 17 Nonlinear optical crystals are processed in a matching direction, according to Figure 3 As shown, the K4B6Si3O4 laser 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 1064 nm. An infrared beam 2 with a wavelength of 1064 nm emitted from the Q-switched Nd:YAG laser 1 is incident on the K4B6Si3O4 laser. 17 Nonlinear optical crystal 3 produces green frequency-doubled light with a wavelength of 532 nm, and the output intensity is about 1.4 times that of KDP under the same conditions.

[0099] Example 65 The arbitrary K4B6Si3O obtained in Examples 45-63 17 Nonlinear optical crystals are processed in a matching direction, according to Figure 3 As shown, the laser is positioned at position 3. At room temperature, a Q-switched Nd:YAG laser is used as the light source with an incident wavelength of 532 nm. An infrared beam 2 with a wavelength of 532 nm is emitted from the Q-switched Nd:YAG laser 1 and enters the nonlinear optical crystal 3, producing frequency-doubled light with a wavelength of 266 nm. The output intensity is approximately 0.2 times that of BBO under the same conditions.

[0100] The above are merely preferred embodiments of the present invention, but the scope of protection of the present invention is not limited thereto. Any variations or substitutions that can be easily conceived by those skilled in the art within the scope of the technology disclosed in the present invention should be included within the scope of protection of the present invention.

Claims

1. A compound, potassium borosilicate, characterized in that, The chemical formula of this compound is K4B6Si3O 17 Its molecular weight is 577.

53.

2. A method for preparing potassium borosilicate as described in claim 1, characterized in that, Prepared using solid-state synthesis or vacuum encapsulation methods; When preparing potassium borosilicate using a solid-phase synthesis method, the steps are as follows: The potassium borosilicate compound is obtained by mixing the K-containing compound, the B-containing compound and the Si-containing compound in a molar ratio of K:B:Si = 4:6:3 and keeping the mixture at a constant temperature of 550-850℃ for 24-120 hours. When preparing potassium borosilicate using the vacuum encapsulation method, the steps are as follows: The K-containing compound, the B-containing compound, and the Si-containing compound are mixed uniformly in a molar ratio of K:B:Si = 4:6:

3. Under vacuum conditions, the temperature is increased to 600-850 ℃ at a rate of 5-10 ℃ / h and held at the temperature for 24-120 hours to obtain the compound potassium borosilicate.

3. The method for preparing potassium borosilicate according to claim 2, characterized in that, The K-containing compound is selected from KOH, K2CO3, KNO3, KHCO3 or K2SiO3; the B-containing compound is H3BO3 or B2O3; and the Si-containing compound is SiO2 or H2SiO3.

4. A potassium borosilicate nonlinear optical crystal, characterized in that, The chemical formula of this crystal is K4B6Si3O 17 It has a molecular weight of 577.53, belongs to the monoclinic crystal system, and has a space group of C 2. The unit cell parameters are a = 11.8628(13) Å, b = 6.6285(6) Å, c = 11.0097(19) Å, β = 117.183(4)°, unit cell volume is 770.10(17) Å 3 .

5. A method for preparing the potassium borosilicate nonlinear optical crystal according to claim 4, characterized in that, Crystals are grown using the melt method, high-temperature melt method, vacuum encapsulation method, hydrothermal method, or room temperature solution method. When growing potassium borosilicate nonlinear optical crystals using the melt method, the specific operation is as follows: a. Mix the K-containing compound, the B-containing compound and the Si-containing compound in a molar ratio of K:B:Si = 4:6:3 until homogeneous, and keep at a constant temperature of 700-900 ℃ for 24-120 hours to obtain potassium borosilicate powder. b. The potassium borosilicate powder prepared in step a is kept at 700-900 ℃ for 10-120 hours to obtain a mixed melt; c. The mixed melt obtained in step b is cooled to 650 ℃ at a rate of 0.1-2 ℃ / h, and then cooled to room temperature at a rate of 5-10 ℃ / h to obtain potassium borosilicate seed crystals. d. Fix the potassium borosilicate seed crystal obtained in step c onto the seed crystal rod, lower the seed crystal from above the mixed melt obtained in step b, apply a crystal rotation of 2-20 rpm through the crystal growth controller, pull the seed crystal at a speed of 1-10 mm / day, and simultaneously cool it down at a rate of 0.1-10 ℃ / h. After the crystal growth stops, the potassium borosilicate nonlinear optical crystal is obtained. Alternatively, fix the potassium borosilicate seed crystal obtained in step c onto a seed crystal rod, lower the seed crystal from above the mixed melt obtained in step b, and cool it at a rate of 0.1-10 ℃ / h to allow the crystal to grow for 5-15 hours. Slowly raise the crystal without removing it from the liquid surface to continue growing. Repeat this process until the crystal growth stops, and you will obtain a potassium borosilicate nonlinear optical crystal. Alternatively, place the potassium borosilicate seed crystal prepared in step c at the bottom of the crucible, then put the potassium borosilicate powder prepared in step a into the crucible, seal the platinum crucible, raise the temperature of the growth furnace to 700-900 ℃, keep the temperature constant for 10-120 hours, adjust the position of the crucible to make the seed crystal slightly melt, and then lower the crucible at a rate of 1-10 mm / day while keeping the growth temperature constant, or lower it to 650 ℃ at the fastest cooling rate of 3 ℃ / h. After the growth is completed, lower it to room temperature at a rate of 5-10 ℃ / h to obtain the potassium borosilicate nonlinear optical crystal. When growing potassium borosilicate nonlinear optical crystals using the high-temperature melt method, the specific operation is as follows: a. Mix the K-containing compound, the B-containing compound and the Si-containing compound in a molar ratio of K:B:Si = 4:6:3 until homogeneous, and keep at a constant temperature of 700-900 ℃ for 24-120 hours to obtain potassium borosilicate powder. b. Mix the potassium borosilicate powder obtained in step a with a flux at a molar ratio of 1:(0.1-6) until homogeneous, and keep the mixture at 700-900 ℃ for 5-120 hours to obtain a mixed melt; c. Preparation of seed crystals: The mixed melt obtained in step b is cooled to 650 ℃ at a rate of 0.1-2 ℃ / h, and then cooled to room temperature at a rate of 5-10 ℃ / h to obtain potassium borosilicate seed crystals. d. Crystal growth: Fix the potassium borosilicate seed crystal obtained in step c onto the seed crystal rod, lower the seed crystal from above the mixed melt obtained in step b, apply a crystal rotation of 2-20 rpm, and cool down at a rate of 0.1-3 ℃ / h. After the crystal growth stops, the potassium borosilicate nonlinear optical crystal is obtained. When growing potassium borosilicate nonlinear optical crystals using the vacuum encapsulation method, the specific operation is as follows: a. Mix the K-containing compound, the B-containing compound and the Si-containing compound in a molar ratio of K:B:Si = 4:6:3 until homogeneous, and keep at a constant temperature of 650-850 ℃ for 24-120 hours to obtain potassium borosilicate powder. b. Mix the potassium borosilicate powder obtained in step a with a flux at a molar ratio of (0.1-1):(0.1-6) until homogeneous, heat to 650-850 ℃, hold at that temperature for 5-120 hours, then cool to 650 ℃ at a rate of 0.1-3 ℃ / h, and then cool to room temperature at a rate of 5-10 ℃ / h to obtain the potassium borosilicate nonlinear optical crystal. When growing potassium borosilicate nonlinear optical crystals using the hydrothermal method, the specific operation is as follows: a. Mix the K-containing compound, the B-containing compound and the Si-containing compound in a molar ratio of K:B:Si = 4:6:3 until homogeneous, heat to 600-850 ℃, and hold at the temperature for 24-120 hours to obtain potassium borosilicate powder. b. Place the potassium borosilicate powder obtained in step a into water, sonicate it, and adjust the pH to 8-11 with HF and KOH to obtain a mixed solution; c. Under sealed conditions, the mixed solution obtained in step b is heated to 450-600 ℃, kept at the temperature for 5-8 days, and then cooled to room temperature at a cooling rate of 5-20 ℃ / day to obtain potassium borosilicate nonlinear optical crystal. When growing potassium borosilicate nonlinear optical crystals using the room temperature solution method, the specific operation is as follows: a. Mix the K-containing compound, the B-containing compound and the Si-containing compound in a molar ratio of K:B:Si = 4:6:3 until homogeneous, heat to 700-900 ℃, and hold at the temperature for 24-120 hours to obtain potassium borosilicate powder. b. Add the potassium borosilicate powder obtained in step a to water, dissolve it by sonication, adjust the pH to 8-11 with HF and KOH, and filter to obtain a mixed solution; c. Place the mixed solution obtained in step b in a clean glass 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 the water in the aqueous solution. Let it stand at room temperature for 5-20 days. d. When crystal particles grow at the bottom of the container from the solution in step c, until the size of the crystal particles no longer changes significantly, seed crystals are obtained. e. Select a seed crystal with a clean, flat, uncontaminated, and crack-free surface from step d, suspend it in the mixed solution prepared in step b, and allow it to grow at room temperature for 10-30 days to obtain a potassium borosilicate nonlinear optical crystal.

6. The method for preparing potassium borosilicate nonlinear optical crystal according to claim 5, characterized in that, The K-containing compound is selected from KOH, K2CO3, KNO3, KHCO3 or K2SiO3; the B-containing compound is H3BO3 or B2O3; and the Si-containing compound is SiO2 or H2SiO3.

7. The method for preparing potassium borosilicate nonlinear optical crystal according to claim 5, characterized in that, The flux is selected from H3BO3, B2O3, PbO or PbF2.

8. The use of the potassium borosilicate nonlinear optical crystal as described in claim 4 in the fabrication of a frequency multiplier, an up or down frequency converter, or an optical parametric oscillator.

9. The use of the potassium borosilicate nonlinear optical crystal as described in claim 4 in preparing harmonic light output at harmonics of 2nd, 3rd, 4th, and 5th harmonics from the 1064 nm fundamental frequency light output by an Nd:YAG laser.

10. Use of a potassium borosilicate nonlinear optical crystal as described in claim 4 in the preparation of deep ultraviolet frequency-doubled light output below 200 nm.

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