Chlorinated guanidinium acetate nonlinear optical crystal, method of preparation and use

Abstract

This invention relates to a nonlinear optical crystal of guanidinoacetic acid chloride, its preparation method, and its uses. The crystal has the molecular formula C3N3O2H8Cl, a molecular weight of 153.57, belongs to the tetragonal crystal system, and has a space group of [missing information]. I 2 d The unit cell parameters are a =15.7150(13)Å, b =15.7150(13)Å, c =11.0742(15)Å, α =90.00° β =90.00° gamma =90.00° Z =16, V =2734.9(6)Å 3 Centimeter-sized crystals were grown using evaporation, aqueous solution cooling, or hydrothermal methods. Under 1064 nm laser irradiation, the crystal exhibited a frequency doubling response similar to that of potassium dihydrogen phosphate. The ultraviolet absorption edge of the crystal was approximately 250 nm, and the experimental birefringence was approximately 0.08 at 546 nm. This crystal preparation method is simple and low-cost, possesses significant nonlinear optical effects, a large birefringence, a wide transmission range, and is easy to grow and process. It can be used as an ultraviolet nonlinear optical crystal and a birefringent crystal.

Description

Technical Field

[0001] This invention relates to guanidinoacetic acid chloride nonlinear optical crystals, their preparation methods, and their uses. Background Technology

[0002] Lasers are playing an increasingly important role in scientific research, industry, transportation, national defense, medical and health care, and information technology. Due to the limitations of laser working materials, lasers can usually only output laser light within a limited wavelength range. Therefore, using nonlinear optical crystals to perform frequency doubling, sum-frequency, difference-frequency, and optical parametric oscillations on the fundamental frequency light output by existing lasers is an important means of obtaining coherent light in the ultraviolet and other wavelength ranges.

[0003] Currently, nonlinear optical crystal materials mainly fall into two categories: inorganic nonlinear optical crystals and organic nonlinear optical crystals. Organic nonlinear optical crystals typically possess high molecular hyperpolarizability, high birefringence, and good designability, attracting widespread attention in the field of novel frequency conversion materials. However, some existing organic nonlinear optical crystals still suffer from problems such as demanding crystal growth conditions, difficulty in scaling up dimensions, insufficient physicochemical stability, or limited processing performance.

[0004] Therefore, developing a novel organic nonlinear optical crystal that is easy to grow, can produce crystals at the centimeter scale or larger, and has a large nonlinear optical effect and a large birefringence is of great significance for expanding the ultraviolet frequency conversion material system and promoting the application of related devices. Summary of the Invention

[0005] One of the objectives of this invention is to provide a nonlinear optical crystal of guanidinoacetic acid chloride.

[0006] The second objective of this invention is to provide a method for preparing a nonlinear optical crystal of guanidinoacetic acid chloride.

[0007] The third objective of this invention is to provide the use of guanidinoacetic acid chloride nonlinear optical crystals in ultraviolet nonlinear optical devices and birefringent devices.

[0008] The present invention discloses a nonlinear optical crystal of guanidinoacetic acid chloride, which has the chemical formula C3N3O2H8Cl, a molecular weight of 153.57, belongs to the tetragonal crystal system, and has a space group of [missing information]. I 2 d The unit cell parameters are a =15.7150(13)Å, b =15.7150(13)Å, c =11.0742(15)Å, α =90.00° β =90.00° γ =90.00°Z =16, V =2734.9(6)Å 3 The crystal exhibits a frequency doubling response under 1064nm laser irradiation, with an ultraviolet absorption edge of approximately 250nm and an experimental birefringence of approximately 0.08@546nm.

[0009] The method for preparing the guanidinoacetic acid nonlinear optical crystal uses guanidinoacetic acid and hydrochloric acid as starting materials and employs evaporation, aqueous solution cooling, or hydrothermal methods to prepare the guanidinoacetic acid nonlinear optical crystal. The crystal growth method using evaporation is specifically performed according to the following steps: a. Mix guanidinoacetic acid and hydrochloric acid at a molar ratio of 1:1-3, place them in a polytetrafluoroethylene beaker, plastic beaker or glass beaker, add 20-100 mL of deionized water, stir or sonicate for 5-30 minutes to fully dissolve and form a clear solution; b. After filtering the solution obtained in step a, transfer it into a crystallization container, seal it with plastic wrap, and then poke several small holes at the seal to adjust the evaporation rate. c. Place the crystallization container at a temperature of 20-30℃ and allow it to evaporate. After the size of the precipitated crystals no longer changes, remove the crystals and dry them to obtain guanidinoacetic acid chloride nonlinear optical crystals. The crystal growth method using aqueous solution cooling is performed according to the following steps: a. Mix guanidinoacetic acid and hydrochloric acid at a molar ratio of 1:1-3, place them in a polytetrafluoroethylene beaker, plastic beaker or glass beaker, add 20-100mL of deionized water, heat to 40-80℃, and stir until the raw materials are completely dissolved to obtain a saturated or near-saturated solution. b. Filter the solution obtained in step a while hot and transfer it to a crystallization container. Slowly cool the temperature from 40-80℃ to 20-30℃ and maintain the low cooling rate until crystals precipitate. c. After the crystal grows to the target size, remove the crystal and dry it to obtain the guanidinoacetic acid nonlinear optical crystal. The hydrothermal crystal growth method is specifically performed according to the following steps: a. Mix guanidinoacetic acid and hydrochloric acid evenly at a molar ratio of 1:1-3, transfer the mixture into a clean, uncontaminated 23-100mL high-temperature and high-pressure reactor liner, add 0.5-6mL of deionized water, and tighten and seal the reactor. b. Place the high-temperature and high-pressure reactor from step a into a constant temperature chamber, raise it to 80-180℃ at a rate of 10-30℃ / h, keep it at the constant temperature for 2-10 days, and then lower it to room temperature at a rate of 0.1-2℃ / day. c. Open the reaction vessel, take out the crystal and dry it to obtain the guanidinoacetic acid nonlinear optical crystal.

[0010] The application of the guanidinoacetic acid chloride nonlinear optical crystal in the preparation of 2nd, 3rd, and 4th harmonic output of the 1064nm fundamental frequency light from an Nd:YAG laser.

[0011] The use of the guanidinoacetic acid chloride nonlinear optical crystal in the preparation of ultraviolet frequency-doubled light output at or below 266 nm.

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

[0013] In the method described in this invention, the hydrochloric acid can be concentrated hydrochloric acid or an aqueous solution of hydrochloric acid. The glass beakers, polytetrafluoroethylene (PTFE) beakers, and plastic beakers used in the evaporation method, aqueous solution cooling method, and hydrothermal method are first acid-washed, then rinsed with deionized water and dried before use; the reactor lining used in the hydrothermal method is a PTFE lining or an inert corrosion-resistant lining.

[0014] By enlarging the size of the crystallization container and extending the crystal growth period, nonlinear optical crystals of guanidinoacetic acid (guanidine chloride) at the centimeter scale and above can be obtained. After being oriented according to crystallographic data, the large-sized crystals are cut and polished, and can then be used as nonlinear optical devices or birefringent optical devices. Attached Figure Description

[0015] Figure 1 The powder XRD pattern is the result of calculations and experiments on guanidinoacetic acid crystals according to the present invention. Figure 2 This is a structural diagram of the guanidinoacetic acid crystal of the present invention; Figure 3 This is a schematic diagram of the working principle of the nonlinear optical device made of guanidinoacetic acid crystal of the present invention, wherein 1 is a laser, 2 is the emitted beam, 3 is guanidinoacetic acid crystal, 4 is the emitted beam, and 5 is a filter. Detailed Implementation

[0016] 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 The evaporation method for crystal growth is performed according to the following steps:

[0017] a. Mix guanidinoacetic acid and hydrochloric acid in a molar ratio of 1:1, place the mixture in a polytetrafluoroethylene beaker, add 20 mL of deionized water, and sonicate for 5 minutes to fully dissolve and form a clear solution. b. After filtering the solution obtained in step a, transfer it into a crystallization container, seal it with plastic wrap, and then poke several small holes at the seal to adjust the evaporation rate. c. Place the crystallization container at 20℃ and allow it to evaporate. Once the size of the precipitated crystal no longer changes, remove the crystal and dry it to obtain a nonlinear optical crystal of guanidinoacetic acid with a size of 15mm×13mm×11mm. Example 2 The evaporation method for crystal growth is performed according to the following steps:

[0018] a. Mix guanidinoacetic acid and hydrochloric acid at a molar ratio of 1:1.5, place the mixture in a polyglass beaker, add 60 mL of deionized water, and sonicate for 20 minutes to fully dissolve and form a clear solution. b. After filtering the solution obtained in step a, transfer it into a crystallization container, seal it with plastic wrap, and then poke several small holes at the seal to adjust the evaporation rate. c. Place the crystallization container at 25℃ and let it evaporate. After the size of the precipitated crystal no longer changes, take out the crystal and dry it to obtain a nonlinear optical crystal of guanidinoacetic acid with a size of 14mm×10mm×8mm. Example 3 The crystal growth method using evaporation is specifically performed according to the following steps:

[0019] a. Mix guanidinoacetic acid and hydrochloric acid in a molar ratio of 1:2, place in a plastic beaker, add 100 mL of deionized water, and sonicate for 30 minutes to fully dissolve and form a clear solution; b. After filtering the solution obtained in step a, transfer it into a crystallization container, seal it with plastic wrap, and then poke several small holes at the seal to adjust the evaporation rate. c. Place the crystallization container at 30℃ and allow it to evaporate. Once the size of the precipitated crystal no longer changes, remove the crystal and dry it to obtain a nonlinear optical crystal of guanidinoacetic acid with a size of 11mm×9mm×7mm. Example 4

[0020] The crystal growth method using aqueous solution cooling is performed according to the following steps: a. Mix guanidinoacetic acid and hydrochloric acid in a molar ratio of 1:1-3, place in a glass beaker, add 20 mL of deionized water, heat to 40 °C, and stir until the raw materials are completely dissolved to obtain a nearly saturated solution; b. Filter the solution obtained in step a while hot and transfer it to a crystallization container. Slowly cool the solution from 40°C to 20°C and maintain the low cooling rate until crystals precipitate. c. After the crystal grows to the target size, remove the crystal and dry it to obtain a nonlinear optical crystal of guanidinoacetic acid chloride with a size of 10mm×10mm×6mm. Example 5

[0021] The crystal growth method using aqueous solution cooling is performed according to the following steps: a. Mix guanidinoacetic acid and hydrochloric acid at a molar ratio of 1:1.5, place the mixture in a polytetrafluoroethylene beaker, add 60 mL of deionized water, heat to 70 °C, and stir until the raw materials are completely dissolved to obtain a saturated solution; b. Filter the solution obtained in step a while hot and transfer it to a crystallization container. Slowly cool the solution from 70°C to 30°C and maintain the low cooling rate until crystals precipitate. c. After the crystal grows to the target size, remove the crystal and dry it to obtain a nonlinear optical crystal of guanidinoacetic acid chloride with a size of 8mm×7mm×6mm. Example 6

[0022] The crystal growth method using aqueous solution cooling is performed according to the following steps: a. Mix guanidinoacetic acid and hydrochloric acid in a molar ratio of 1:2, place the mixture in a plastic beaker, add 100 mL of deionized water, heat to 80 °C, and stir until the raw materials are completely dissolved to obtain a saturated solution; b. Filter the solution obtained in step a while hot and transfer it to a crystallization container. Slowly cool the solution from 80°C to 20°C and maintain the low cooling rate until crystals precipitate. c. After the crystal grows to the target size, remove the crystal and dry it to obtain a nonlinear optical crystal of guanidinoacetic acid chloride with a size of 9mm×9mm×6mm. Example 7

[0023] The hydrothermal method for crystal growth is performed according to the following steps: a. Mix guanidinoacetic acid and hydrochloric acid evenly at a molar ratio of 1:1, transfer the mixture into a clean, uncontaminated 23mL high-temperature and high-pressure reactor liner, add 0.5mL of deionized water, and tighten and seal the reactor. b. Place the high-temperature and high-pressure reactor from step a in a constant temperature chamber, raise it to 180°C at a rate of 10°C / h, keep it at that temperature for 10 days, and then lower it to room temperature at a rate of 0.1°C / day. c. Open the reaction vessel, take out the crystal and dry it to obtain a nonlinear optical crystal of guanidinoacetic acid chloride with a size of 11mm×10mm×7mm. Example 8

[0024] The hydrothermal crystal growth method is specifically performed according to the following steps: a. Mix guanidinoacetic acid and hydrochloric acid evenly at a molar ratio of 1:1.5, transfer the mixture into a clean, uncontaminated 50mL high-temperature and high-pressure reactor liner, add 3mL of deionized water, and tighten and seal the reactor. b. Place the high-temperature and high-pressure reactor from step a in a constant temperature chamber, raise it to 140℃ at a rate of 20℃ / h, keep it at that temperature for 5 days, and then lower it to room temperature at a rate of 0.1℃ / day. c. Open the reaction vessel, take out the crystal and dry it to obtain a nonlinear optical crystal of guanidinoacetic acid chloride with a size of 8mm×8mm×5mm. Example 9

[0025] The hydrothermal method for crystal growth is performed according to the following steps: a. Mix guanidinoacetic acid and hydrochloric acid evenly at a molar ratio of 1:3, transfer the mixture into a clean, uncontaminated 100mL high-temperature and high-pressure reactor liner, add 6mL of deionized water, and tighten and seal the reactor. b. Place the high-temperature and high-pressure reactor from step a into a constant temperature chamber, raise it to 80°C at a rate of 10°C / h, keep it at that temperature for 2 days, and then lower it to room temperature at a rate of 2°C / day. c. Open the reaction vessel, take out the crystal and dry it to obtain a nonlinear optical crystal of guanidinoacetic acid chloride with a size of 5mm×4mm×3mm. Example 10

[0026] Any of the single crystals of guanidinoacetic acid obtained in Examples 1-9 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 1064 nm. When the single crystal was irradiated by the incident infrared beam, a frequency doubling output of 532 nm was obtained, indicating that the crystal has excellent frequency doubling performance. Example 11

[0027] Any of the single crystals of guanidinoacetic acid obtained in Examples 1-9 were processed in matching directions, and a Q-switched Nd:YAG laser was used as the light source at room temperature with an incident wavelength of 532 nm to obtain a frequency-doubled output of 266 nm. Example 12

[0028] After processing any of the single crystals of guanidinoacetic acid obtained in Examples 1-9 in matching directions, they can be used to prepare frequency multipliers, up-frequency converters, down-frequency converters, optical parametric oscillators, ultraviolet nonlinear optical devices, and birefringent devices.

Claims

1. A nonlinear optical crystal of guanidinyl acetic acid chloride, characterized in that, The crystal has the chemical formula C3N3O2H8Cl, a molecular weight of 153.57, belongs to the tetragonal crystal system, and has a space group of [space group number missing]. I 2 d The unit cell parameters are a =15.7150(13)Å, b =15.7150(13)Å, c =11.0742(15)Å, α =90.00° β =90.00° γ =90.00° Z =16, V =2734.9(6)Å 3 The crystal exhibits a frequency doubling response under 1064nm laser irradiation, with an ultraviolet absorption edge of approximately 250nm and an experimental birefringence of 0.08@546nm.

2. A method for preparing a nonlinear optical crystal of guanidinoacetic acid chloride as described in claim 1, characterized in that: Nonlinear optical crystals of guanidinoacetic acid chloride were prepared using guanidinoacetic acid and hydrochloric acid as starting materials by evaporation, aqueous solution cooling, or hydrothermal methods. The crystal growth method using evaporation is specifically performed according to the following steps: a. Mix guanidinoacetic acid and hydrochloric acid at a molar ratio of 1:1-3, place them in a polytetrafluoroethylene beaker, plastic beaker or glass beaker, add 20-100 mL of deionized water, stir or sonicate for 5-30 minutes to fully dissolve and form a clear solution; b. After filtering the solution obtained in step a, transfer it into a crystallization container, seal it with plastic wrap, and then poke several small holes at the seal to adjust the evaporation rate. c. Place the crystallization container at a temperature of 20-30℃ and allow it to evaporate. After the size of the precipitated crystals no longer changes, remove the crystals and dry them to obtain guanidinoacetic acid chloride nonlinear optical crystals. The crystal growth method using aqueous solution cooling is performed according to the following steps: a. Mix guanidinoacetic acid and hydrochloric acid at a molar ratio of 1:1-3, place them in a polytetrafluoroethylene beaker, plastic beaker or glass beaker, add 20-100mL of deionized water, heat to 40-80℃, and stir until the raw materials are completely dissolved to obtain a saturated or near-saturated solution. b. Filter the solution obtained in step a while hot and transfer it to a crystallization container. Slowly cool the temperature from 40-80℃ to 20-30℃ and maintain the low cooling rate until crystals precipitate. c. After the crystal grows to the target size, remove the crystal and dry it to obtain the guanidinoacetic acid nonlinear optical crystal. The hydrothermal crystal growth method is specifically performed according to the following steps: a. Mix guanidinoacetic acid and hydrochloric acid evenly at a molar ratio of 1:1-3, transfer the mixture into a clean, uncontaminated 23-100mL high-temperature and high-pressure reactor liner, add 0.5-6mL of deionized water, and tighten and seal the reactor. b. Place the high-temperature and high-pressure reactor from step a into a constant temperature chamber, raise it to 80-180℃ at a rate of 10-30℃ / h, keep it at the constant temperature for 2-10 days, and then lower it to room temperature at a rate of 0.1-2℃ / day. c. Open the reaction vessel, take out the crystal and dry it to obtain the guanidinoacetic acid nonlinear optical crystal.

3. The use of the guanidinoacetic acid chloride nonlinear optical crystal as described in claim 1 in preparing second, third, and fourth harmonic light output from the 1064nm fundamental frequency light of an Nd:YAG laser.

4. The use of the guanidinoacetic acid chloride nonlinear optical crystal as described in claim 1 in the preparation of ultraviolet frequency-doubled light output at or below 266 nm.

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

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