Cesium hydroxyfluoroborate nonlinear optical crystal, method of making and use

Abstract

This invention relates to a cesium hydroxyfluoroborate nonlinear optical crystal, its preparation method, and its uses. The crystal has the molecular formula CsB3O3F2(OH)2, belongs to the orthorhombic crystal system, and has the space group [missing information]. PCA 21, molecular weight 285.4, unit cell parameters are a =15.333(3)Å, b =6.176(4) Å, c =14.373(3)Å, α =90.00° β =90.00° c =90.00° Z =8, V =1361.1Å 3 The crystals are grown using room-temperature solvent evaporation or hydrothermal methods. This series of crystals has an ultraviolet transmission cutoff edge below 190 nm and an experimental birefringence of approximately 0.08 at 546 nm. The crystal preparation method is simple and low-cost, exhibiting significant nonlinear optical effects, a large birefringence, a wide transmission range, and ease of growth and processing. It can be used as an ultraviolet nonlinear optical crystal and a birefringent crystal.

Description

Technical Field

[0001] This invention relates to the field of inorganic functional crystal materials technology, specifically to a cesium hydroxyfluoroborate nonlinear optical crystal, its preparation method, and its applications. Background Technology

[0002] Laser technology has a wide range of applications in scientific research, industry, national defense, medicine, and information technology. Due to the limitations of the laser working material, lasers can usually only output laser light within a limited wavelength range. Therefore, it is often necessary to use nonlinear optical crystals to perform frequency conversion such as frequency doubling, sum frequency conversion, and difference frequency conversion on the fundamental frequency light to obtain coherent ultraviolet or even deep ultraviolet light.

[0003] Borate systems have long been an important research area for ultraviolet and deep ultraviolet nonlinear optical crystals due to their wide transmission range, good chemical stability, and large nonlinear optical response. Fluorohydrate-containing borates and fluorohydroxyborates, in particular, have seen significant advancements due to the introduction of fluorine... − and OH − These groups often possess both a short ultraviolet cutoff edge and a large birefringence, making them promising candidates for application in the field of ultraviolet nonlinear optics.

[0004] However, some existing ultraviolet nonlinear optical crystals still suffer from problems such as demanding preparation conditions, long crystal growth cycles, high equipment requirements, and difficulty in obtaining high-quality, large-size crystals at low cost. Therefore, it is of great significance to develop a novel crystal material that can be grown under mild conditions via room-temperature solvent evaporation or hydrothermal methods, while exhibiting good ultraviolet transmittance, high birefringence, and considerable nonlinear optical effects. Summary of the Invention

[0005] The purpose of this invention is to provide a cesium hydroxyfluoroborate nonlinear optical crystal, the chemical formula of which is CsB3O3F2(OH)2.

[0006] Another objective of this invention is to provide a method for preparing a cesium hydroxyfluoroborate nonlinear optical crystal, wherein the crystal is grown using a room-temperature solvent evaporation method or a hydrothermal method.

[0007] Another object of the present invention is to provide the use of the aforementioned cesium hydroxyfluoroborate nonlinear optical crystal in ultraviolet nonlinear optical devices and birefringent devices.

[0008] The invention discloses a cesium hydroxyfluoroborate nonlinear optical crystal, characterized in that the crystal has the molecular formula CsB3O3F2(OH)2, belongs to the orthorhombic crystal system, and has a space group of [missing information]. Pca 21. For CsB3O3F2(OH)2, the molecular weight is 285.4, and the unit cell parameters are... a =15.333(3)Å, b =6.176(4) Å,c =14.373(3)Å, α =90.00° β =90.00° γ =90.00° Z =8, V =1361.1Å 3 .

[0009] The method for preparing a cesium hydroxyfluoroborate nonlinear optical crystal involves growing the crystal using either a room-temperature solvent evaporation method or a hydrothermal method. The crystal growth method using room-temperature solvent evaporation is performed according to the following steps: a. Mix the following raw materials: CsOH / HBF4 / H3BO3 system, Cs2CO3 / HBF4 / H3BO3 system, CsHCO3 / HBF4 / H3BO3 system, CsNO3 / HF / H3BO3 system, CsBF4 / H3BO3 system, CsBF4 / HBO2 / H3BO3 system, or CH3COOCs / HF / H3BO3 system, and place them in a polytetrafluoroethylene beaker, plastic beaker, or glass beaker; b. Add 20-100 mL of deionized water to the mixture obtained in step a, and sonicate for 5-30 minutes to ensure thorough mixing and dissolution; c. Seal the polytetrafluoroethylene beaker, plastic beaker or glass beaker containing the solution with plastic wrap, and then poke several small holes in the seal to adjust the evaporation rate. Place it at a temperature of 20-30℃ and let it evaporate until the size of the crystals precipitated at the bottom of the beaker no longer changes. Take out the crystals and dry them to obtain CsB3O3F2(OH)2 nonlinear optical crystal. The hydrothermal crystal growth method is specifically performed according to the following steps: a. After thoroughly mixing the raw materials CsOH / HBF4 / H3BO3 system, Cs2CO3 / HBF4 / H3BO3 system, CsHCO3 / HBF4 / H3BO3 system, CsNO3 / HF / H3BO3 system, CsBF4 / H3BO3 system, CsBF4 / HBO2 / H3BO3 system, or CH3COOCs / HF / H3BO3 system, transfer the mixture into a clean, uncontaminated 23-100mL high-temperature and high-pressure reactor liner for further mixing. b. Add 0.5-6 mL of deionized water to the mixture obtained in step a, and tighten and seal the reaction vessel; c. Place the reactor from step b in a constant temperature chamber, raise the temperature to 180-220℃ at a rate of 20℃ / h, hold the temperature for 5-7 days, and then lower the temperature to room temperature at a rate of 1℃ / day. Open the reactor to obtain the CsB3O3F2(OH)2 nonlinear optical crystal.

[0010] The application of the cesium hydroxyfluoroborate nonlinear optical crystal in the preparation of 2nd, 3rd, 4th and 5th harmonic output of the 1064nm fundamental frequency light output by the Nd:YAG laser.

[0011] The use of the series of tetrafluorohydroxyborate nonlinear optical crystals in the preparation of ultraviolet frequency-doubled light output at or below 266 nm.

[0012] The use of the cesium hydroxyfluoroborate nonlinear optical crystal in the fabrication of frequency multiplier generators, up or down frequency converters, or optical parametric oscillators.

[0013] The cesium hydroxyfluoroborate nonlinear optical crystal described in this invention is easy to grow, transparent and unencapsulated, and has the advantages of fast growth rate, low cost, and easy acquisition of large-size crystals.

[0014] The containers used in the preparation process described in this invention are glass beakers, polytetrafluoroethylene (PTFE) beakers, plastic beakers, and high-pressure reactors with PTFE liners. Before use, the glass beakers, PTFE beakers, and plastic beakers are first cleaned with acid, then rinsed with deionized water and dried.

[0015] The CsB3O3F2(OH)2 crystal obtained by the method described in this invention can be used as a nonlinear optical device or a birefringent optical device after the crystal blank is oriented according to crystallographic data, the crystal is cut according to the required angle, thickness and cross-sectional size, and the light-transmitting surface of the crystal is polished. Attached Figure Description

[0016] Figure 1 This is the powder XRD pattern of the cesium hydroxyfluoroborate nonlinear optical crystal of the present invention; Figure 2 This is a structural diagram of the cesium hydroxyfluoroborate nonlinear optical crystal of the present invention; Figure 3 This is a schematic diagram of the working principle of the nonlinear optical device fabricated by the cesium hydroxyfluoroborate nonlinear optical crystal of the present invention, wherein 1 is a laser, 2 is the emitted beam, 3 is the cesium hydroxyfluoroborate nonlinear optical crystal, 4 is the emitted beam, and 5 is a filter. Detailed Implementation

[0017] The present invention will now be described in detail with reference to the accompanying drawings and specific embodiments. The following description should not be construed as limiting the scope of protection of the present invention, and any improvements made based on the present invention will not depart from its spirit. Unless otherwise specified, the raw materials or equipment used in the present invention are commercially available. Example 1

[0018] Preparation of CsB3O3F2(OH)2 nonlinear optical crystals by room temperature solvent evaporation: Prepared using the chemical reaction CsOH + HBF4 + 2H3BO3 → CsB3O3F2(OH)2 + 2HF + 2H2O: a. Mix CsOH, HBF4 and H3BO3 in a molar ratio of 1:1:2 and place them in a polytetrafluoroethylene beaker; b. Add 20 mL of deionized water to the mixture obtained in step a, and sonicate for 5 minutes to ensure thorough mixing and dissolution; c. Seal the beaker containing the solution with plastic wrap, and then poke several small holes in the seal to adjust the evaporation rate. Place the beaker at 20°C and let it evaporate until the size of the crystals precipitated at the bottom of the beaker no longer changes. This yields a CsB3O3F2(OH)2 nonlinear optical crystal with dimensions of 4mm×2mm×2mm. Example 2

[0019] Preparation of CsB3O3F2(OH)2 nonlinear optical crystal by room temperature solvent evaporation: Prepared using the chemical reaction Cs₂CO₃ + 2HBF₄ + 4H₃BO₃ → 2CsB₃O₃F₂(OH)₂ + CO₂↑ + 4HF + 3H₂O: a. Mix Cs2CO3, HBF4 and H3BO3 in a molar ratio of 1:2:4 and place in a glass beaker; b. Add 60 mL of deionized water to the mixture obtained in step a, and sonicate for 10 minutes to ensure thorough mixing and dissolution; c. Seal the glass beaker containing the solution with plastic wrap, and then poke several small holes in the seal to adjust the evaporation rate. Place the glass beaker at a temperature of 25°C and let it evaporate until the size of the crystals precipitated at the bottom of the glass beaker no longer changes, thus obtaining a CsB3O3F2(OH)2 nonlinear optical crystal with a size of 3mm×2mm×2mm. Example 3

[0020] Preparation of CsB3O3F2(OH)2 nonlinear optical crystal by room temperature solvent evaporation: Prepared using the chemical reaction CsHCO3 + HBF4 + 2H3BO3 → CsB3O3F2(OH)2 + CO2↑ + 2HF + 2H2O: a. Mix CsHCO3, HBF4 and H3BO3 in a molar ratio of 1:1:2 and place in a plastic beaker; b. Add 100 mL of deionized water to the mixture obtained in step a, and sonicate for 20 minutes to ensure thorough mixing and dissolution; c. Seal the plastic beaker containing the solution with plastic wrap, and then poke several small holes in the seal to adjust the evaporation rate. Place the plastic beaker at a temperature of 30°C and let it evaporate until the size of the crystals precipitated at the bottom of the plastic beaker no longer changes, thus obtaining a CsB3O3F2(OH)2 nonlinear optical crystal with dimensions of 4mm×2mm×1mm. Example 4

[0021] Preparation of CsB3O3F2(OH)2 nonlinear optical crystals by room temperature solvent evaporation: Prepared using the chemical reaction CsNO3 + 2HF + 3H3BO3 → CsB3O3F2(OH)2 + HNO3 + 4H2O: a. Mix CsNO3, HF and H3BO3 in a molar ratio of 1:2:3 and place in a polytetrafluoroethylene beaker; b. Add 20 mL of deionized water to the mixture obtained in step a, and sonicate for 15 minutes to ensure thorough mixing and dissolution; c. Seal the polytetrafluoroethylene beaker containing the solution with plastic wrap, and then poke several small holes in the seal to adjust the evaporation rate. Place the polytetrafluoroethylene beaker at a temperature of 20°C and let it evaporate until the size of the crystals precipitated at the bottom of the polytetrafluoroethylene beaker no longer changes, thus obtaining a CsB3O3F2(OH)2 nonlinear optical crystal with a size of 2mm×1mm×1mm. Example 5

[0022] Preparation of CsB3O3F2(OH)2 nonlinear optical crystal by room temperature solvent evaporation: Prepared using the chemical reaction CsBF4 + 2H3BO3 → CsB3O3F2(OH)2 + 2HF + H2O: a. Mix CsBF4 and H3BO3 in a molar ratio of 1:2 and place in a plastic beaker; b. Add 60 mL of deionized water to the mixture obtained in step a, and sonicate for 25 minutes to ensure thorough mixing and dissolution; c. Seal the plastic beaker containing the solution with plastic wrap, and then poke several small holes in the seal to adjust the evaporation rate. Place the plastic beaker at a temperature of 25°C and let it evaporate until the size of the crystals precipitated at the bottom of the plastic beaker no longer changes, thus obtaining a CsB3O3F2(OH)2 nonlinear optical crystal with a size of 3mm×2mm×2mm. Example 6

[0023] Preparation of CsB3O3F2(OH)2 nonlinear optical crystal by room temperature solvent evaporation: Prepared using the chemical reaction CsBF4 + HBO2 + H3BO3 → CsB3O3F2(OH)2 + 2HF: a. Mix CsBF4, HBO2 and H3BO3 in a molar ratio of 1:1:1 and place in a plastic beaker; b. Add 100 mL of deionized water to the mixture obtained in step a, and sonicate for 30 minutes to ensure thorough mixing and dissolution; c. Seal the plastic beaker containing the solution with plastic wrap, and then poke several small holes in the seal to adjust the evaporation rate. Place the plastic beaker at a temperature of 30°C and let it evaporate until the size of the crystals precipitated at the bottom of the plastic beaker no longer changes, thus obtaining a CsB3O3F2(OH)2 nonlinear optical crystal with a size of 2mm×1mm×1mm. Example 7

[0024] Preparation of CsB3O3F2(OH)2 nonlinear optical crystal by room temperature solvent evaporation: Prepared using the chemical reaction CH3COOCs + 2HF + 3H3BO3 → CsB3O3F2(OH)2 + CH3COOH + 4H2O: a. Mix CH3COOCs, HF and H3BO3 in a molar ratio of 1:2:3 and place in a glass beaker; b. Add 80 mL of deionized water to the mixture obtained in step a, and sonicate for 25 minutes to ensure thorough mixing and dissolution; c. Seal the glass beaker containing the solution with plastic wrap, and then poke several small holes in the seal to adjust the evaporation rate. Place the glass beaker at a temperature of 25°C and let it evaporate until the size of the crystals precipitated at the bottom of the beaker no longer changes, thus obtaining a CsB3O3F2(OH)2 nonlinear optical crystal with a size of 2mm×2mm×1mm. Example 8

[0025] Preparation of CsB3O3F2(OH)2 nonlinear optical crystals by hydrothermal method: Prepared using the chemical reaction CsOH + HBF4 + 2H3BO3 → CsB3O3F2(OH)2 + 2HF + 2H2O: a. Mix CsOH, HBF4 and H3BO3 evenly in a molar ratio of 1:1:2, and transfer the mixture into the lining of a 23mL high-temperature and high-pressure reactor; b. Add 0.5 mL of deionized water to the mixture obtained in step a, and tighten and seal the reaction vessel; c. Place the high-pressure reactor from step b in a constant temperature chamber, raise the temperature to 180°C at a rate of 20°C / h, hold the temperature for 7 days, and then lower the temperature to room temperature at a rate of 1°C / day. Open the reactor to obtain a CsB3O3F2(OH)2 nonlinear optical crystal with dimensions of 2mm×2mm×1mm. Example 9

[0026] Preparation of CsB3O3F2(OH)2 nonlinear optical crystals by hydrothermal method: Prepared using the chemical reaction Cs₂CO₃ + 2HBF₄ + 4H₃BO₃ → 2CsB₃O₃F₂(OH)₂ + CO₂↑ + 4HF + 3H₂O: a. Mix Cs2CO3, HBF4 and H3BO3 evenly in a molar ratio of 1:2:4 and then transfer the mixture into the lining of a 50mL high-temperature and high-pressure reactor. b. Add 3 mL of deionized water to the mixture obtained in step a, and tighten and seal the reaction vessel; c. Place the high-pressure reactor from step b into a constant temperature chamber, raise the temperature to 200℃ at a rate of 20℃ / h, hold the temperature for 6 days, and then lower it to room temperature at a rate of 1℃ / day. Open the reactor to obtain a CsB3O3F2(OH)2 nonlinear optical crystal with dimensions of 1mm×1mm×1mm. Example 10

[0027] Preparation of CsB3O3F2(OH)2 nonlinear optical crystals by hydrothermal method: Prepared using the chemical reaction CsHCO3 + HBF4 + 2H3BO3 → CsB3O3F2(OH)2 + CO2↑ + 2HF + 2H2O: a. Mix CsHCO3, HBF4, and H3BO3 thoroughly in a molar ratio of 1:1:2, and transfer the mixture into the lining of a 100mL high-temperature and high-pressure reactor. b. Add 6 mL of deionized water to the mixture obtained in step a, and tighten and seal the reaction vessel; c. Place the high-pressure reactor from step b into a constant temperature chamber, raise the temperature to 220°C at a rate of 20°C / h, hold the temperature for 5 days, and then lower the temperature to room temperature at a rate of 1°C / day. Open the reactor to obtain a CsB3O3F2(OH)2 nonlinear optical crystal with dimensions of 2mm×1mm×1mm. Example 11

[0028] Preparation of CsB3O3F2(OH)2 nonlinear optical crystals by hydrothermal method: Prepared using the chemical reaction CsNO3 + 2HF + 3H3BO3 → CsB3O3F2(OH)2 + HNO3 + 4H2O: After mixing CsNO3, HF and H3BO3 evenly in a molar ratio of 1:2:3, the mixture is transferred into the lining of a 23mL high-temperature and high-pressure reactor. b. Add 0.5 mL of deionized water to the mixture obtained in step a, and tighten and seal the reaction vessel; c. Place the high-pressure reactor from step b in a constant temperature chamber, raise the temperature to 180°C at a rate of 20°C / h, hold the temperature for 7 days, and then lower the temperature to room temperature at a rate of 1°C / day. Open the reactor to obtain a CsB3O3F2(OH)2 nonlinear optical crystal with dimensions of 1mm×1mm×1mm. Example 12

[0029] Preparation of CsB3O3F2(OH)2 nonlinear optical crystals by hydrothermal method: Prepared using the chemical reaction CsBF4 + 2H3BO3 → CsB3O3F2(OH)2 + 2HF + H2O: a. Mix CsBF4 and H3BO3 evenly at a molar ratio of 1:2, and transfer the mixture into the lining of a 50mL high-temperature and high-pressure reactor; b. Add 3 mL of deionized water to the mixture obtained in step a, and tighten and seal the reaction vessel; c. Place the high-pressure reactor from step b into a constant temperature chamber, raise the temperature to 200℃ at a rate of 20℃ / h, hold the temperature for 6 days, and then lower it to room temperature at a rate of 1℃ / day. Open the reactor to obtain a CsB3O3F2(OH)2 nonlinear optical crystal with dimensions of 2mm×2mm×1mm. Example 13

[0030] Preparation of CsB3O3F2(OH)2 nonlinear optical crystals by hydrothermal method: Prepared using the chemical reaction CsBF4 + HBO2 + H3BO3 → CsB3O3F2(OH)2 + 2HF: a. Mix CsBF4, HBO2 and H3BO3 evenly in a molar ratio of 1:1:1, and transfer the mixture into the lining of a 100mL high-temperature and high-pressure reactor; b. Add 6 mL of deionized water to the mixture obtained in step a, and tighten and seal the reaction vessel; c. Place the high-pressure reactor in a constant temperature chamber, raise the temperature to 220℃ at a rate of 20℃ / h, hold the temperature for 5 days, and then lower the temperature to room temperature at a rate of 1℃ / day. Open the reactor to obtain a CsB3O3F2(OH)2 nonlinear optical crystal with dimensions of 1mm×1mm×1mm. Example 14

[0031] Preparation of CsB3O3F2(OH)2 nonlinear optical crystals by hydrothermal method: Prepared using the chemical reaction CH3COOCs + 2HF + 3H3BO3 → CsB3O3F2(OH)2 + CH3COOH + 4H2O: a. After mixing CH3COOCs, HF and H3BO3 evenly in a molar ratio of 1:2:3, transfer the mixture into the lining of a 50mL high-temperature and high-pressure reactor. b. Add 3 mL of deionized water to the mixture obtained in step a, and tighten and seal the reaction vessel; c. Place the high-pressure reactor in a constant temperature chamber, raise the temperature to 200℃ at a rate of 20℃ / h, hold the temperature for 6 days, and then lower the temperature to room temperature at a rate of 1℃ / day. Open the reactor to obtain a CsB3O3F2(OH)2 nonlinear optical crystal with dimensions of 2mm×1mm×1mm. Example 15

[0032] Any of the CsB3O3F2(OH)2 nonlinear optical crystals obtained in Examples 1-14 are processed in matching directions. At room temperature, using a Q-switched Nd:YAG laser as the light source with an incident wavelength of 1064nm, a frequency-doubled output of 532nm can be obtained. Example 16

[0033] Any of the CsB3O3F2(OH)2 nonlinear optical crystals obtained in Examples 1-14 were processed in matching directions. At room temperature, a Q-switched Nd:YAG laser was used as the light source, with an incident wavelength of 532nm, to obtain a 266nm frequency-doubled output. Example 17

[0034] After processing any of the CsB3O3F2(OH)2 nonlinear optical crystals obtained in Examples 1-14 in matching directions, they can be used for the second, third, fourth, or fifth harmonic output of 1064nm fundamental frequency light, or for the preparation of frequency multiplier generators, up-frequency converters, down-frequency converters, optical parametric oscillators, ultraviolet nonlinear optical devices, and birefringent devices.

Claims

1. A cesium hydroxyfluoroborate nonlinear optical crystal, characterized in that, The molecular formula of this crystal is CsB3O3F2(OH)2, it belongs to the orthorhombic crystal system, and its space group is [missing information]. Pca 21. For CsB3O3F2(OH)2, the molecular weight is 285.4, and the unit cell parameters are... a =15.333(3)Å, b =6.176(4) Å, c =14.373(3)Å, α =90.00° β =90.00° γ =90.00° Z =8, V =1361.1Å 3 It is produced by room temperature solvent evaporation or hydrothermal method.

2. The method for preparing a cesium hydroxyfluoroborate nonlinear optical crystal as described in claim 1, characterized in that, Crystals are grown using either room-temperature solvent evaporation or hydrothermal methods. The crystal growth method using room-temperature solvent evaporation is performed according to the following steps: a. Mix the following raw materials: CsOH / HBF4 / H3BO3 system, Cs2CO3 / HBF4 / H3BO3 system, CsHCO3 / HBF4 / H3BO3 system, CsNO3 / HF / H3BO3 system, CsBF4 / H3BO3 system, CsBF4 / HBO2 / H3BO3 system, or CH3COOCs / HF / H3BO3 system, and place them in a polytetrafluoroethylene beaker, plastic beaker, or glass beaker; b. Add 20-100 mL of deionized water to the mixture obtained in step a, and sonicate for 5-30 minutes to ensure thorough mixing and dissolution; c. Seal the polytetrafluoroethylene beaker, plastic beaker or glass beaker containing the solution with plastic wrap, and then poke several small holes in the seal to adjust the evaporation rate. Place it at a temperature of 20-30℃ and let it evaporate until the size of the crystals precipitated at the bottom of the beaker no longer changes. Take out the crystals and dry them to obtain CsB3O3F2(OH)2 nonlinear optical crystal. The hydrothermal crystal growth method is specifically performed according to the following steps: a. After thoroughly mixing the raw materials CsOH / HBF4 / H3BO3 system, Cs2CO3 / HBF4 / H3BO3 system, CsHCO3 / HBF4 / H3BO3 system, CsNO3 / HF / H3BO3 system, CsBF4 / H3BO3 system, CsBF4 / HBO2 / H3BO3 system, or CH3COOCs / HF / H3BO3 system, transfer the mixture into a clean, uncontaminated 23-100mL high-temperature and high-pressure reactor liner for further mixing. b. Add 0.5-6 mL of deionized water to the mixture obtained in step a, and tighten and seal the reaction vessel; c. Place the reactor from step b in a constant temperature chamber, raise the temperature to 180-220℃ at a rate of 20℃ / h, hold the temperature for 5-7 days, and then lower the temperature to room temperature at a rate of 1℃ / day. Open the reactor to obtain the CsB3O3F2(OH)2 nonlinear optical crystal.

3. The use of the cesium hydroxyfluoroborate nonlinear optical crystal as described in claim 1 in the preparation of second, third, fourth, and fifth harmonic output of the 1064nm fundamental frequency light output by an Nd:YAG laser.

4. The use of the series of tetrafluorohydroxyborate nonlinear optical crystals as described in claim 1 in the preparation of ultraviolet frequency-doubled light output at or below 266 nm.

5. The use of the cesium hydroxyfluoroborate nonlinear optical crystal as described in claim 1 in the fabrication of frequency doubling generators, up or down frequency converters, or optical parametric oscillators.

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