Patent Grant
10662067
This application is the national phase entry of International Application No. PCT/CN2017/074336, filed on Feb. 22, 2017, which is based upon and claims priority to Chinese Patent Application No. 201611128283.3, filed on Dec. 9, 2016, the entire contents of which are incorporated herein by reference.
The present invention relates to a compound ammonium fluoroborate NH4B4O6F, a nonlinear optical crystal of ammonium fluoroborate NH4B4O6F, and a preparation method and use thereof.
Recently, with the strong demand for the deep-ultraviolet laser source (generally refers to the laser source emitting a laser with a wavelength of shorter than 200 nm) of 193 nm lithography technology, micro-nano fine laser processing, and modern instruments such as ultra-high energy resolution photoelectron spectrometer and photoelectron emission microscopy, developing an all-solid-state deep-ultraviolet laser source has become a research hotspot of the international laser scientific community. The deep-ultraviolet nonlinear optical crystal is a key element to develop the all-solid-state deep-ultraviolet laser source.
Currently, the ultraviolet and deep-ultraviolet nonlinear optical crystals used in the industries mainly include LiB3O5 (LBO), CsB3O5 (CBO), CsLiB6O10 (CLBO), BaB2O4 (BBO), and KBe2BO3F2(KBBF) crystals. LBO crystal has a wide transmission region, a good optical homogeneity, a large effective frequency multiplication factor (3KDP) and a high damage threshold (18.9 GW/cm2). However, LBO crystal is unable to achieve phase matching in the deep-ultraviolet region due to its relatively small birefringence (Δn=0.04-0.05) and the shortest second harmonic wavelength is 276 nm. Similar to LBO crystal, CBO and CLBO crystals also have limited applications in the deep-ultraviolet region due to the relatively small birefringence. Although BBO crystal has a large frequency-doubling coefficient and a large birefringence, its relatively high ultraviolet absorption cutoff edge (189 nm) and the shortest second harmonic wavelength of 204.8 nm limit its application in the deep-ultraviolet region. KBBF can output a frequency-sextupled light from a 1064 nm fundamental wavelength directly; however, it is difficult to grow a large-sized crystal due to the layered growth habit of KBBF, which limits its application to some extent. Therefore, there is an urgent need to develop a new deep-ultraviolet nonlinear optical crystal with good comprehensive performances.
One object of the present invention is to provide a compound ammonium fluoroborate with a chemical formula of NH4B4O6F and a molecular weight of 176.28. The compound is prepared using a solid phase reaction process.
Another object of the present invention is to provide a nonlinear optical crystal of ammonium fluoroborate NH4B4O6F, with a chemical formula of NH4B4O6F and a molecular weight of 176.28, and the crystal belongs to an orthorhombic system, with a space group of Pna21, and has the following unit cell parameters: a=7.615(3) Å, b=11.207(4) Å, c=6.604(3) Å, Z=4, V=563.6 Å3.
Yet another object of the present invention is to provide a method for preparing the nonlinear optical crystal of ammonium fluoroborate NH4B4O6F and use thereof.
The compound ammonium fluoroborate of the present invention has a chemical formula of NH4B4O6F and a molecular weight of 176.28, and prepared by a solid phase reaction process.
The method for preparing the compound ammonium fluoroborate comprises the steps of:
mixing an NH4-containing compound, a Boron-containing compound, and a Fluorine-containing compound evenly at a molar ratio of NH4:B:F=(0.5-2):(3-5):(0.5-2), sealing the mixture in a hydrothermal reactor or a quartz tube, placing the hydrothermal reactor or the quartz tube into a muffle furnace or a drying oven, raising the temperature to 150-580° C. at a rate of 20-40° C./h and keeping the temperature for 10-48 h, then reducing the temperature to 30° C. at a rate of 1-10° C./h, and opening the hydrothermal reactor or the quartz tube to obtain the compound NH4B4O6F; wherein the NH4-containing compound is NH4F, the Boron-containing compound is H3BO3 and B2O3, and the Fluorine-containing compound is NH4F or HF.
The present invention provides a nonlinear optical crystal of ammonium fluoroborate with a chemical formula of NH4B4O6F and a molecular weight of 176.28, which belongs to an orthorhombic system, with a space group of Pna21, and has the following cell parameters: a=7.615(3) Å, b=11.207(4) Å, c=6.604(3) Å, Z=4, V=563.6 Å3.
The methods for preparing the nonlinear optical crystal of ammonium fluoroborate include a flux method, a Bridgman-Stockbarger method, a room temperature solution method and a solvothermal method.
Said room temperature solution method for growing the nonlinear optical crystal of ammonium fluoroborate comprises the following steps:
a. mixing an NH4-containing compound, a Boron-containing compound, and a Fluorine-containing compound evenly at a molar ratio of NH4:B:F=(0.5-2):(3-5):(0.5-2), sealing the mixture in a hydrothermal reactor or a quartz tube, placing the hydrothermal reactor or the quartz tube into a muffle furnace or a drying oven, raising the temperature to 150-580° C. at a rate of 20-40° C./h and keeping the temperature for 10-48 h, then reducing the temperature to 30° C. at a rate of 1-10° C./h, and opening the hydrothermal reactor or the quartz tube and removing the product to obtain the compound NH4B4O6F;
wherein the NH4-containing compound is NH4F, the Boron-containing compound is H3BO3 or B2O3, and the Fluorine-containing compound is NH4F or HF;
b. sealing the compound NH4B4O6F obtained in step a in a hydrothermal reactor or a quartz tube, placing the hydrothermal reactor or the quartz tube into a muffle furnace or a drying oven, raising the temperature to 200-600° C. at a rate of 20-40° C./h and keeping the temperature for 10-48 h, then reducing the temperature to 30° C. at a rate of 1-5° C./h, and opening the hydrothermal reactor or the quartz tube to obtain a seed crystal of NH4B4O6F;
c. placing the seed crystal obtained in step b at the bottom of a container, and then placing the compound NH4B4O6F obtained in step a into the container;
d. sealing the container in step c or sealing the container in step c after the addition of 10-100 mL of a solvent, placing the container into a muffle furnace or a drying oven, raising the temperature to 150-600° C. at a rate of 20-40° C./h and keeping the temperature for 10-48 h, then reducing the temperature to 50° C. at a rate of 1-3° C./day, and then reducing the temperature to 30° C. at a rate of 1-10° C./h, and opening the container to obtain the nonlinear optical crystal of NH4B4O6F with a size of 1-20 mm; wherein the solvent is deionized water, anhydrous ethanol, N,N-dimethylformamide, N,N-dimethylacetamide or hydrofluoric acid.
Said flux method for growing the nonlinear optical crystal of ammonium fluoroborate comprises the following steps:
a. mixing an NH4-containing compound, a Boron-containing compound, and an Fluorine-containing compound evenly at a molar ratio of NH4:B:F=(0.5-2):(3-5):(0.5-2), sealing the mixture in a hydrothermal reactor or a quartz tube, placing the hydrothermal reactor or the quartz tube into a muffle furnace or a drying oven, raising the temperature to 150-580° C. at a rate of 20-40° C./h and keeping the temperature for 10-48 h, then reducing the temperature to 30° C. at a rate of 1-10° C./h, and opening the hydrothermal reactor or the quartz tube to obtain the compound NH4B4O6F;
wherein the NH4-containing compound is NH4F, the Boron-containing compound is H3BO3 or B2O3, and the Fluorine-containing compound is NH4F or HF;
b. sealing the compound NH4B4O6F obtained in step a in a hydrothermal reactor or a quartz tube, placing the hydrothermal reactor or the quartz tube into a muffle furnace or a drying oven, raising the temperature to 200-600° C. at a rate of 20-40° C./h and keeping the temperature for 10-48 h, then reducing the temperature to 30° C. at a rate of 1-5° C./h, and opening the hydrothermal reactor or the quartz tube to obtain a seed crystal of NH4B4O6F;
c. placing the seed crystal of NH4B4O6F obtained in step b at the bottom of a quartz tube, then mixing the compound NH4B4O6F obtained in step a with a flux at a molar ratio of 1:(1-10) and placing the mixture into the quartz tube, and the tube was lame-sealed under 10−3 Pa with a flame gun; wherein the flux is NH4F, NH4F:H3BO3, NH4F:B2O3, H3BO3 or B2O3;
d. sealing the quartz tube in step c or sealing the quartz tube in step c after the addition of 10-100 mL of a solvent, placing the quartz tube into a muffle furnace or a drying oven, raising the temperature to 150-600° C. at a rate of 20-40° C./h and keeping the temperature for 10-48 h, then reducing the temperature to 50° C. at a rate of 1-3° C./day, and then reducing the temperature to 30° C. at a rate of 1-10° C./h, and opening the container and removing the product to obtain the nonlinear optical crystal of NH4B4O6F with a size of 1-20 mm; wherein the solvent is deionized water, anhydrous ethanol, N,N-dimethylformamide, N,N-dimethylacetamide or hydrofluoric acid.
Said Bridgman-Stockbarger method for growing the nonlinear optical crystal of ammonium fluoroborate comprises the following steps:
a. mixing an NH4-containing compound, a Boron-containing compound, and an Fluorine-containing compound evenly at a molar ratio of NH4:B:F=(0.5-2):(3-5):(0.5-2), sealing the mixture in a hydrothermal reactor or a quartz tube, placing the hydrothermal reactor or the quartz tube into a muffle furnace or a drying oven, raising the temperature to 150-580° C. at a rate of 20-40° C./h and keeping the temperature for 10-48 h, then reducing the temperature to 30° C. at a rate of 1-10° C./h, and opening the hydrothermal reactor or the quartz tube and removing the product to obtain the compound NH4B4O6F;
wherein the NH4-containing compound is NH4F, the Boron-containing compound is H3BO3 or B2O3, and the Fluorine-containing compound is NH4F or HF;
b. sealing the compound NH4B4O6F obtained in step a in a hydrothermal reactor or a quartz tube, placing the hydrothermal reactor or the quartz tube into a muffle furnace or a drying oven, raising the temperature to 200-600° C. at a rate of 20-40° C./h and keeping the temperature for 10-48 h, then reducing the temperature to 30° C. at a rate of 1-5° C./h, and opening the hydrothermal reactor or the quartz tube to obtain a seed crystal of NH4B4O6F;
c. placing the seed crystal obtained in step b at the bottom of a container, and then placing the compound NH4B4O6F obtained in step a into the container;
d. sealing the container in step c and placing the container into a Bridgman-Stockbarger furnace, raising the temperature to 300-600° C. and keeping the temperature for 10-20 h, adjusting the position of the container to allow the compound NH4B4O6F to spontaneously nucleate or inoculate at 350-600° C., then lowering the container at a rate of 0.05-2 mm/h slowly while keeping the growth temperature constant or reducing the temperature slowly at a rate of 0-3° C./h, then reducing the temperature of the furnace to 30° C. after the growth of the crystal is completed, and removing the container to obtain the nonlinear optical crystal of NH4B4O6F with a size of 1-20 mm.
Said solvothermal method for growing the nonlinear optical crystal of ammonium fluoroborate comprises the following steps:
a. mixing an NH4-containing compound, a Boron-containing compound, and a Fluorine-containing compound evenly at a molar ratio of NH4:B:F=(0.5-2):(3-5):(0.5-2), sealing the mixture in a hydrothermal reactor or a quartz tube, placing the hydrothermal reactor or the quartz tube into a muffle furnace or a drying oven, raising the temperature to 150-580° C. at a rate of 20-40° C./h and keeping the temperature for 10-48 h, then reducing the temperature to 30° C. at a rate of 1-10° C./h, and opening the hydrothermal reactor or the quartz tube to obtain the compound NH4B4O6F;
wherein the NH4-containing compound is NH4F, the Boron-containing compound is H3BO3 or B2O3, and the Fluorine-containing compound is NH4F or HF;
b. sealing the compound NH4B4O6F obtained in step a in a hydrothermal reactor or a quartz tube, placing the hydrothermal reactor or the quartz tube into a muffle furnace or a drying oven, raising the temperature to 200-600° C. at a rate of 20-40° C./h and keeping the temperature for 10-48 h, then reducing the temperature to 30° C. at a rate of 1-5° C./h, and opening the hydrothermal reactor or the quartz tube to obtain a seed crystal of NH4B4O6F:
c. placing the seed crystal obtained in step b at the bottom of a container, and then placing the compound NH4B4O6F obtained in step a into the container;
d. adding 10-100 mL of a solvent to the container in step c, then subjecting the mixture to ultrasonication to make the mixture mix and dissolve thoroughly, adjusting the pH value of the mixture to pH=1-11, performing filtration with a qualitative filter paper, then sealing the container with a polyvinyl chloride film in which several small holes are punched to adjust the volatilization rate of the solvent in the solution, and placing the container into a static environment without shaking, pollution and air convection, and leaving the mixture to stand at room temperature to allow the crystal to grow, so as to obtain the nonlinear optical crystal of NH4B4O6F with a size of 1-20 mm at the end of the crystal growth; wherein the solvent is deionized water, anhydrous ethanol, N,N-dimethylformamide, N,N-dimethylacetamide or hydrofluoric acid.
In step c of the preparation process by the flux method, the molar ratio of NH4F to H3BO3 in the flux system of NH4F—H3BO3 is (1-3):(1-5); and the molar ratio of NH4F to B2O3 in the NH4F—B2O3 system is (1-2):(1-4).
The present invention provides use of the nonlinear optical crystal of ammonium fluoroborate in the production of a frequency-doubled, frequency-tripled, frequency-quadrupled, frequency-quintupled or frequency-sextupled harmonic light from a 1064 nm fundamental light output from a Nd:YAG laser.
The present invention provides use of the nonlinear optical crystal of ammonium fluoroborate in producing a deep-ultraviolet frequency-multiplied light below 200 nm.
The present invention provides use of the nonlinear optical crystal of ammonium fluoroborate in the make of a frequency multiplication generator, a frequency up or down converter or an optical parametric oscillator.
Wherein the container used in the methods is a platinum crucible, iridium crucible, ceramic crucible, quartz tube, conical flask, beaker, or hydrothermal reactor lined with polytetrafluoroethylene or lined with stainless steel with a platinum sleeve. When the container is a quartz tube, vacuumization is required before sealing to avoid the burst of the quartz tube resulting from the gas released in the reaction. When the container is a conical flask or beaker, it needs to be washed with acid, then rinsed with deionized water, and dried.
Seven compounds, that is KB4O6F, RbB4O6F, CsB4O6F, NH4B4O6OH, KB4O6OH, RbB4O6OH and CsB4O6OH can be synthesized on the basis of NH4B4O6F. The seven compounds have similar properties to NH4B4O6F, for example: all of them have nonlinear optical coefficients of approximate 0.5-4 KDP and ultraviolet absorption cutoff edges of less than 200 nm, and can be used to output the frequency-doubled, frequency-tripled, frequency-quadrupled, frequency-quintupled or frequency-sextupled harmonic light based on the 1064 nm fundamental light output from an Nd:YAG laser, or used to output the deep-ultraviolet frequency-multiplied light of below 200 nm.
With the method for preparing the nonlinear optical crystal of ammonium fluoroborate of the present invention, the centimeter-sized nonlinear optical crystal of NH4B4O6F can be obtained and the crystal has no obvious layered growth habit. When a large-sized crucible or container is used and the growth cycle of the crystal is prolonged, the corresponding large-sized nonlinear optical crystal of NH4B4O6F can be obtained. During the growth of the nonlinear optical crystal of NH4B4O6F, the crystal is easy to grow up, transparent and with out inclusion, and has the advantages of high growth rate, low cost, and easy to obtain large-sized crystals and so on.
The large-sized nonlinear optical crystal of NH4B4O6F obtained by the method for preparing the nonlinear optical crystal of ammonium fluoroborate in the present invention can be used as a nonlinear optical device by orienting the raw crystal based on the crystallographic data of the crystal, cutting the crystal according to the desired angle, thickness and sectional size, and polishing the transmission surface of the crystal. The nonlinear optical crystal of NH4B4O6F has the advantages of a wide transmission region, stable physical and chemical properties, a high mechanical hardness, hard to break and deliquesce, easy to cut, polish and preserve and so on.
The present invention will be further described in combination with the following examples. It should be noted that, the following examples are not intended to limit the protection scope of the present invention, and any alternations made based on the present invention do not against the spirit of the present invention. The raw materials or equipment used in the present invention are commercially available unless otherwise stated.
The compound NH4B4O6F was synthesized by the solid phase reaction process based on the reaction equation NH4F+2B2O3→NH4B4O6F.
NH4F and B2O3 were mixed uniformly at a molar ratio of 1:1.5 and placed into a Φ10 mm quartz tube. The quartz tube was vacuumized to reach a vacuum degree of 1×10−3 Pa and sealed with a flame gun, and then placed into a muffle furnace. The temperature was raised to 400° C. at a rate of 30° C./h and kept for 24 h and then reduced to 30° C. at a rate of 6° C./h, and the quartz tube was opened to obtain the compound NH4B4O6F.
The compound NH4B4O6F was synthesized by the solid phase reaction process based on the reaction equation NH4F+4H3BO3→NH4B4O6F+6H2↑.
NH4F and H3BO3 were mixed uniformly at a molar ratio of 1:3.5 and placed into a hydrothermal reactor having a volume of 23 mL and lined with polytetrafluoroethylene. The hydrothermal reactor was screwed tightly to be sealed and then was placed into a drying oven. The temperature was raised to 220° C. at a rate of 35° C./h and kept for 24 h and then reduced to 30° C. at a rate of 6° C./h, and the hydrothermal reactor was opened to obtain the compound NH4B4O6F.
The compound NH4B4O6F was synthesized according to the specific operation steps in Example 1 based on the reaction equation NH4F+2B2O3→NH4B4O6F.
The resultant compound NH4B4O6F was sealed in a hydrothermal reactor and then the hydrothermal reactor was placed into a drying oven. The temperature was raised to 200° C. at a rate of 20° C./h and kept for 10 h and then reduced to 30° C. at a rate of 1° C./h, and the hydrothermal reactor was opened to obtain a seed crystal of NH4B4O6F.
The resultant seed crystal was placed at the bottom of a clean beaker and then the resultant compound NH4B4O6F were placed into the beaker.
10 mL of hydrofluoric acid was added to the beaker as a solvent. The mixture was mixed and dissolved thoroughly by ultrasonication, adjusted to pH=5-6, and filtered with a qualitative filter paper. The beaker was sealed with a polyvinyl chloride film in which several small holes were punched to adjust the volatilization rate of the solvent in the solution, and was placed into a static environment without shaking, pollution and air convection. The mixture was left to stand at room temperature to obtain the NH4B4O6F crystal with a size of 5 mm×6 mm×8 mm at the end of the crystal growth.
The compound NH4B4O6F was synthesized according to the specific operation steps in Example 1 based on the reaction equation NH4F+2B2O3→NH4B4O6F.
The resultant compound NH4B4O6F was placed into a φ10 mm quartz tube. The quartz tube was vacuumized to reach a vacuum degree of 1×10−3 Pa and sealed with a flame gun, and then placed into a muffle furnace. The temperature was raised to 600° C. at a rate of 40° C./h and kept for 48 h and then reduced to 30° C. at a rate of 5° C./h, and the quartz tube was opened to obtain a seed crystal of NH4B4O6F.
The resultant seed crystal was placed at the bottom of a conical flask and then the resultant compound NH4B4O6F were placed into the conical flask.
100 mL of anhydrous ethanol was added to the conical flask. The mixture was mixed and dissolved thoroughly by ultrasonication, and then filtered with a qualitative filter paper. The conical flask was sealed with a polyvinyl chloride film in which several small holes were punched to adjust the volatilization rate of the solvent in the solution, and was placed into a static environment without shaking, pollution and air convection. The mixture was left to stand at room temperature to obtain the NH4B4O6F crystal with a size of 7 mm×6 mm×4 mm at the end of the crystal growth.
The compound NH4B4O6F was synthesized according to the specific operation steps in Example 2 based on the reaction equation NH4F+4H3BO3→NH4B4O6F+6H2↑.
The resultant compound NH4B4O6F was sealed in a hydrothermal reactor. Then the hydrothermal reactor was placed into a drying oven. The temperature was raised to 300° C. at a rate of 30° C./h and kept for 20 h and then reduced to 30° C. at a rate of 2° C./h, and the hydrothermal reactor was opened to obtain a seed crystal of NH4B4O6F.
The resultant seed crystal was placed at the bottom of a beaker and then the compound NH4B4O6F obtained in step a was placed into the beaker.
N,N-dimethylacetamide was added to the beaker. The mixture was mixed and dissolved thoroughly by ultrasonication, and then filtered with a qualitative filter paper. The beaker was sealed with a polyvinyl chloride film in which several small holes were punched to adjust the volatilization rate of the solvent in the solution, and was placed into a static environment without shaking, pollution and air convection. The mixture was left to stand at room temperature to obtain the NH4B4O6F crystal with a size of 13 mm×8 mm×5 mm at the end of the crystal growth.
The compound NH4B4O6F was synthesized according to the specific operation steps in Example 2 based on the reaction equation NH4F+4H3BO3→NH4B4O6F+6H2O↑.
The resultant compound NH4B4O6F was placed into a Φ10 mm quartz tube. The quartz tube was vacuumized to reach a vacuum degree of 1×10−3 Pa and sealed with a flame gun and then placed into a muffle furnace. The temperature was raised to 400° C. at a rate of 30° C./h and kept for 30 h and then reduced to 30° C. at a rate of 2° C./h, and the quartz tube was opened to obtain a seed crystal of NH4B4O6F.
The resultant seed crystal of NH4B4O6F was placed at the bottom of a quartz tube. Then the resultant compound NH4B4O6F and the flux NH4F were mixed at a molar ratio of 1:2, and placed into the quartz tube. The quartz tube was vacuumized to reach a vacuum degree of 1×10−3 Pa and sealed with a flame gun.
Then the quartz tube was placed into a muffle furnace. The temperature was raised to 500° C. at a rate of 30° C./h and kept for 24 h, then reduced to 450° C. at a rate of 1.5° C./day, and then reduced to 30° C. at a rate of 2° C./h, and the quartz tube was cut to obtain the NH4B4O6F crystal with a size of 5 mm×7 mm×9 mm.
The compound NH4B4O6F was synthesized according to the specific operation steps in Example 1 based on the reaction equation NH4F+2B2O3→NH4B4O6F.
The resultant compound NH4B4O6F was placed into a Φ10 mm quartz tube. The quartz tube was vacuumized to reach a vacuum degree of 1×10−3 Pa and sealed with a flame gun and then placed into a muffle furnace. The temperature was raised to 300° C. at a rate of 20° C./h and kept for 10 h and then reduced to 30° C. at a rate of 1° C./h, and the quartz tube was opened to obtain a seed crystal of NH4B4O6F.
The seed crystal of NH4B4O6F was placed at the bottom of a Φ10 mm quartz tube. Then the compound NH4B4O6F and the flux NH4F—H3BO3 (wherein the molar ratio of NH4F to H3BO3 is 1:1) were mixed at a molar ratio of 1:1, and placed into the quartz tube. The quartz tube was vacuumized to reach a vacuum degree of 1×10−3 Pa and sealed with a flame gun.
Then the quartz tube was placed into a muffle furnace. The temperature was raised to 450° C. at a rate of 30° C./h and kept for 24 h, then reduced to 400° C. at a rate of 1.5° C./day, and then reduced to 30° C. at a rate of 2° C./h, and the quartz tube was cut to obtain the NH4B4O6F crystal with a size of 10 mm×7 mm×6 mm.
The compound NH4B4O6F was synthesized according to the specific operation steps in Example 2 based on the reaction equation NH4F+4H3BO3→NH4B4O6F+6H2O↑.
The resultant compound NH4B4O6F was placed into a Φ10 mm quartz tube. The quartz tube was vacuumized to reach a vacuum degree of 1×10−3 Pa and sealed with a flame gun and then placed into a muffle furnace. The temperature was raised to 500° C. at a rate of 40° C./h and kept for 40 h and then reduced to 30° C. at a rate of 4° C./h, and the quartz tube was opened to obtain a seed crystal of NH4B4O6F.
The resultant seed crystal of NH4B4O6F was placed at the bottom of a quartz tube. Then the resultant compound NH4B4O6F and the flux NH4F—B2O3 (the molar ratio of NH4F to B2O3 is 1:4) were mixed at a molar ratio of 1:5, and placed into the quartz tube. The quartz tube was vacuumized to reach a vacuum degree of 1×10−3 Pa and sealed with a flame gun.
Then the quartz tube was placed into a muffle furnace. The temperature was raised to 450° C. at a rate of 40° C./h and kept for 20 h, then reduced to 400° C. at a rate of 2° C./day, and then reduced to 30° C. at a rate of 3° C./h, and the quartz tube was cut to obtain the NH4B4O6F crystal with a size of 5 mm×7 mm×8 mm.
The compound NH4B4O6F was synthesized according to the specific operation steps in Example 1 based on the reaction equation NH4F+2B2O3→NH4B4O6F.
The resultant compound NH4B4O6F was placed into a Φ10 mm quartz tube. The quartz tube was vacuumized to reach a vacuum degree of 1×10−3 Pa and sealed with a flame gun and then placed into a muffle furnace. The temperature was raised to 300° C. at a rate of 25° C./h and kept for 30 h and then reduced to 30° C. at a rate of 3° C./h, and the quartz tube was opened to obtain a seed crystal of NH4B4O6F.
The seed crystal of NH4B4O6F was placed at the bottom of a Φ10 mm quartz tube. Then the compound NH4B4O6F and the flux H3BO3 were mixed at a molar ratio of 1:5, and placed into the quartz tube. The quartz tube was vacuumized to reach a vacuum degree of 1×10−3 Pa and sealed with a flame gun.
Then the quartz tube was placed into a muffle furnace. The temperature was raised to 600° C. at a rate of 40° C./h and kept for 48 h, then reduced to 550° C. at a rate of 3° C./day, and then reduced to 30° C. at a rate of 10° C./h, and the quartz tube was cut to obtain the NH4B4O6F crystal with a size of 8 mm×7 mm×6 mm.
The compound NH4B4O6F was synthesized according to the specific operation steps in Example 1 based on the reaction equation NH4F+2B2O3→NH4B4O6F.
The resultant compound NH4B4O6F was sealed in a hydrothermal reactor and the hydrothermal reactor was placed into a drying oven. The temperature was raised to 200° C. at a rate of 25° C./h and kept for 15 h and then reduced to 30° C. at a rate of 3° C./h, and the hydrothermal reactor was opened to obtain a seed crystal of NH4B4O6F.
The seed crystal of NH4B4O6F was placed at the bottom of a Φ10 mm quartz tube. Then the compound NH4B4O6F and the flux NH4F—H3BO3 (the molar ratio of NH4F to H3BO3 is 2:3) were mixed at a molar ratio of 1:10, and placed into the quartz tube. The quartz tube was vacuumized to reach a vacuum degree of 1×10−3 Pa and sealed with a flame gun.
Then the quartz tube was placed into a muffle furnace. The temperature was raised to 450° C. at a rate of 30° C./h and kept for 24 h, then reduced to 400° C. at a rate of 1.5° C./day, and then reduced to 30° C. at a rate of 2° C./h, and the quartz tube was cut to obtain the NH4B4O6F crystal with a size of 8 mm×6 mm×4 mm.
The compound NH4B4O6F was synthesized according to the specific operation steps in Example 2 based on the reaction equation NH4F+4H3BO3→NH4B4O6F+6H2O↑.
The resultant compound NH4B4O6F was placed into a Φ10 mm quartz tube. The quartz tube was vacuumized to reach a vacuum degree of 1×10−3 Pa and sealed with a flame gun and then placed into a muffle furnace. The temperature was raised to 500° C. at a rate of 40° C./h and kept for 40 h and then reduced to 30° C. at a rate of 4° C./h, and the quartz tube was opened to obtain a seed crystal of NH4B4O6F.
The resultant seed crystal of NH4B4O6F was placed at the bottom of a quartz tube. Then the resultant compound NH4B4O6F and the flux NH4F—B2O3 (the molar ratio of NH4F to B2O3 is 1:4) were mixed at a molar ratio of 1:5, and placed into the quartz tube. The quartz tube was vacuumized to reach a vacuum degree of 1×10−3 Pa and sealed with a flame gun.
Then the quartz tube was placed into a muffle furnace. The temperature was raised to 400° C. at a rate of 40° C./h and kept for 20 h, then reduced to 350° C. at a rate of 2° C./day, and then reduced to 30° C. at a rate of 3° C./h, and the quartz tube was cut to obtain the NH4B4O6F crystal with a size of 5 mm×7 mm×7 mm.
The compound NH4B4O6F was synthesized according to the specific operation steps in Example 1 based on the reaction equation NH4F+2B2O3→NH4B4O6F.
The resultant compound NH4B4O6F was sealed in a hydrothermal reactor and the hydrothermal reactor was placed into a drying oven. The temperature was raised to 200° C. at a rate of 25° C./h and kept for 30 h and then reduced to 30° C. at a rate of 3° C./h, and the hydrothermal reactor was opened to obtain a seed crystal of NH4B4O6F.
The seed crystal of NH4B4O6F was placed at the bottom of a Φ10 mm quartz tube. Then the compound NH4B4O6F and the flux H3BO3 were mixed at a molar ratio of 1:5, and placed into the quartz tube. The quartz tube was vacuumized to reach a vacuum degree of 1×10−3 Pa and sealed with a flame gun.
Then the quartz tube was placed into a muffle furnace. The temperature was raised to 600° C. at a rate of 40° C./h and kept for 48 h, then reduced to 550° C. at a rate of 3° C./day, and then reduced to 30° C. at a rate of 10° C./h, and the quartz tube was cut to obtain the NH4B4O6F crystal with a size of 8 mm×6 mm×4 mm.
The compound NH4B4O6F was synthesized according to the specific operation steps in Example 2 based on the reaction equation NH4F+4H3BO3→NH4B4O6F+6H2O↑.
The resultant compound NH4B4O6F was placed into a Φ10 mm quartz tube. The quartz tube was vacuumized to reach a vacuum degree of 1×10−3 Pa and sealed with a flame gun and then placed into a muffle furnace. The temperature was raised to 550° C. at a rate of 35° C./h and kept for 40 h and then reduced to 30° C. at a rate of 5° C./h, and the quartz tube was opened to obtain a seed crystal of NH4B4O6F.
The resultant seed crystal of NH4B4O6F was placed at the bottom of a quartz tube. Then the resultant compound NH4B4O6F and the flux NH4F—B2O3 (the molar ratio of NH4F to B2O3 is 2:4) were mixed at a molar ratio of 1:5, and placed into the quartz tube. The quartz tube was vacuumized to reach a vacuum degree of 1×10−3 Pa and sealed with a flame gun.
Then the quartz tube was placed into a muffle furnace. The temperature was raised to 450° C. at a rate of 35° C./h and kept for 36 h, then reduced to 400° C. at a rate of 4° C./day, and then reduced to 30° C. at a rate of 10° C./h, and the quartz tube was cut to obtain the NH4B4O6F crystal with a size of 5 mm×7 mm×9 mm.
The compound NH4B4O6F was synthesized according to the specific operation steps in Example 1 based on the reaction equation NH4F+2B2O3→NH4B4O6F.
The resultant compound NH4B4O6F was placed into a Φ10 mm quartz tube. The quartz tube was vacuumized to reach a vacuum degree of 1×10−3 Pa and sealed with a flame gun and then placed into a muffle furnace. The temperature was raised to 550° C. at a rate of 40° C./h and kept for 25 h and then reduced to 30° C. at a rate of 4° C./h, and the quartz tube was cut to obtain a seed crystal of NH4B4O6F.
The seed crystal of NH4B4O6F was placed at the bottom of a Φ10 mm quartz tube. Then the compound NH4B4O6F and the flux NH4F—H3BO3 (the molar ratio of NH4F to H3BO3 is 3:5) were mixed at a molar ratio of 1:10, and placed into the quartz tube. The quartz tube was vacuumized to reach a vacuum degree of 1×10−3 Pa and sealed with a flame gun.
Then the quartz tube was placed into a muffle furnace. The temperature was raised to 550° C. at a rate of 40° C./h and kept for 40 h, then reduced to 500° C. at a rate of 3° C./day, and then reduced to 30° C. at a rate of 8° C./h, and the quartz tube was cut to obtain the NH4B4O6F crystal with a size of 9 mm×7 mm×6 mm.
The compound NH4B4O6F was synthesized according to the specific operation steps in Example 1 based on the reaction equation NH4F+2B2O3→NH4B4O6F.
The resultant compound NH4B4O6F was placed into a Φ10 mm quartz tube. The quartz tube was vacuumized to reach a vacuum degree of 1×10−3 Pa and sealed with a flame gun and then placed into a muffle furnace. The temperature was raised to 500° C. at a rate of 30° C./h and kept for 15 h and then reduced to 30° C. at a rate of 5° C./h, and the hydrothermal reactor or the quartz tube was opened to obtain a seed crystal of NH4B4O6F.
The seed crystal of NH4B4O6F was placed at the bottom of a Φ10 mm quartz tube. Then the compound NH4B4O6F and the flux B2O3 were mixed at a molar ratio of 1:10, and placed into the quartz tube. The quartz tube was vacuumized to reach a vacuum degree of 1×10−3 Pa and sealed with a flame gun.
Then the quartz tube was placed into a muffle furnace. The temperature was raised to 500° C. at a rate of 40° C./h and kept for 45 h, then reduced to 450° C. at a rate of 3° C./day, and then reduced to 30° C. at a rate of 6° C./h, and the quartz tube was cut to obtain the NH4B4O6F crystal with a size of 7 mm×6 mm×4 mm.
The compound NH4B4O6F was synthesized according to the specific operation steps in Example 1 based on the reaction equation NH4F+2B2O3→NH4B4O6F.
The resultant compound NH4B4O6F was placed into a Φ10 mm quartz tube. The quartz tube was vacuumized to reach a vacuum degree of 1×10−3 Pa and sealed with a flame gun and then placed into a muffle furnace. The temperature was raised to 600° C. at a rate of 40° C./h and kept for 48 h and then reduced to 30° C. at a rate of 5° C./h, and the hydrothermal reactor or the quartz tube was opened to obtain a seed crystal of NH4B4O6F.
The resultant seed crystal was placed at the bottom of a platinum crucible and then the resultant compound NH4B4O6F were placed into the platinum crucible.
The platinum crucible was sealed and placed into a Bridgman-Stockbarger furnace. The temperature was raised to 300° C. and kept for 10 h. The position of the platinum crucible was adjusted to allow the compound NH4B4O6F to nucleate spontaneously. Then the platinum crucible was lowered at a rate of 0.05 mm/h slowly while the growth temperature was kept constant. The temperature of the furnace was reduced to 30° C. after the growth of the crystal is completed, and the platinum crucible was removed to obtain the NH4B4O6F crystal with a size of 6 mm×8 mm×12 mm.
The compound NH4B4O6F was synthesized according to the specific operation steps in Example 1 based on the reaction equation NH4F+4H3BO3→NH4B4O6F+6H2O↑.
The resultant compound NH4B4O6F was sealed in a hydrothermal reactor, and the hydrothermal reactor was placed into a drying oven. The temperature was raised to 200° C. at a rate of 20° C./h and kept for 10 h and then reduced to 30° C. at a rate of 1° C./h, and the hydrothermal reactor was opened to obtain a seed crystal of NH4B4O6F.
The resultant seed crystal was placed at the bottom of an iridium crucible and then the resultant compound NH4B4O6F were placed into the iridium crucible.
The iridium crucible was sealed and placed into a Bridgman-Stockbarger furnace. The temperature was raised to 600° C. and kept for 20 h. The position of the iridium crucible was adjusted to allow the compound NH4B4O6F to inoculate at 350° C. Then the iridium crucible was lowered at a rate of 2 mm/h slowly while the temperature was reduced slowly at a rate of 3° C./h. The temperature of the furnace was reduced to 30° C. after the growth of the crystal is completed, and the iridium crucible was removed to obtain the NH4B4O6F crystal with a size of 7 mm×6 mm×5 mm.
The compound NH4B4O6F was synthesized according to the specific operation steps in Example 1 based on the reaction equation NH4F+2B2O3→NH4B4O6F.
The resultant compound NH4B4O6F was placed into a Φ10 mm quartz tube. The quartz tube was vacuumized to reach a vacuum degree of 1×10−3 Pa and sealed with a flame gun and then placed into a muffle furnace. The temperature was raised to 400° C. at a rate of 30° C./h and kept for 36 h and then reduced to 30° C. at a rate of 3° C./h, and the quartz tube was cut to obtain a seed crystal of NH4B4O6F.
The resultant seed crystal was placed at the bottom of a ceramic crucible and then the resultant compound NH4B4O6F were placed into the ceramic crucible.
The ceramic crucible was sealed and placed into a Bridgman-Stockbarger furnace. The temperature was raised to 400° C. and kept for 15 h. The position of the ceramic crucible was adjusted to allow the compound NH4B4O6F to inoculate at 500° C. Then the ceramic crucible was lowered at a rate of 0.5 mm/h slowly while the growth temperature was kept constant. The temperature of the furnace was reduced to 30° C. after the growth of the crystal is completed, and the ceramic crucible was removed to obtain the NH4B4O6F crystal with a size of 6 mm×8 mm×12 mm.
The compound NH4B4O6F was synthesized according to the specific operation steps in Example 1 based on the reaction equation NH4F+4H3BO3→NH4B4O6F+6H2O↑.
The resultant compound NH4B4O6F was sealed in a hydrothermal reactor and the hydrothermal reactor was placed into a drying oven. The temperature was raised to 200° C. at a rate of 20° C./h and kept for 10 h and then reduced to 30° C. at a rate of 1° C./h, and the hydrothermal reactor was opened to obtain a seed crystal of NH4B4O6F.
The resultant seed crystal was placed at the bottom of a quartz tube and then the resultant compound NH4B4O6F were placed into the quartz tube.
The quartz tube was vacuumized to reach a vacuum degree of 1×10−3 Pa and sealed with a flame gun. Then the quartz tube was placed into a Bridgman-Stockbarger furnace. The temperature was raised to 600° C. and kept for 20 h. The position of the quartz tube was adjusted to allow the compound NH4B4O6F to inoculate at 600° C. Then the quartz tube was lowered at a rate of 1 mm/h slowly while the temperature was reduced slowly at a rate of 2° C./h. The temperature of the furnace was reduced to 30° C. after the growth of the crystal is completed, and the quartz tube was removed to obtain the NH4B4O6F crystal with a size of 7 mm 6 mm×5 mm.
The compound NH4B4O6F was synthesized according to the specific operation steps in Example 2 based on the reaction equation NH4F+4H3BO3→NH4B4O6F+6H2O↑.
The resultant compound NH4B4O6F was sealed in a hydrothermal reactor and the hydrothermal reactor was placed into a drying oven. The temperature was raised to 200° C. at a rate of 20° C./h and kept for 10 h and then reduced to 30° C. at a rate of 1° C./h, and the hydrothermal reactor was opened to obtain a seed crystal of NH4B4O6F.
The resultant seed crystal was placed at the bottom of the polytetrafluoroethylene lining of a hydrothermal reactor having a volume of 23 mL, and then the resultant compound NH4B4O6F was placed into the polytetrafluoroethylene lining.
The solvent of deionized water was added to the polytetrafluoroethylene lining. The hydrothermal reactor was screwed tightly to be sealed and then was placed into a drying oven. The temperature was raised to 150° C. at a rate of 20° C./h and kept for 24 h, then reduced to 100° C. at a rate of 2° C./day and then reduced to 30° C. at a rate of 2° C./h, and the hydrothermal reactor was opened to obtain the NH4B4O6F crystal with a size of 5 mm×6 mm×8 mm.
The compound NH4B4O6F was synthesized according to the specific operation steps in Example 2 based on the reaction equation NH4F+4H3BO3→NH4B4O6F+6H2O↑.
The resultant compound NH4B4O6F was placed at the bottom of the polytetrafluoroethylene lining of a hydrothermal reactor having a volume of 23 mL, and the hydrothermal reactor was placed into a drying oven. The temperature was raised to 200° C. at a rate of 20° C./h and kept for 10 h and then reduced to 30° C. at a rate of 1° C./h, and the hydrothermal reactor was opened to obtain a seed crystal of NH4B4O6F.
The resultant seed crystal was placed at the bottom of the polytetrafluoroethylene lining of a hydrothermal reactor, and then the resultant compound NH4B4O6F was placed into the polytetrafluoroethylene lining of the hydrothermal reactor.
The solvent of 10 mL N,N-dimethylformamide was added to the polytetrafluoroethylene lining of the hydrothermal reactor. The hydrothermal reactor was screwed tightly to be sealed and then was placed into a drying oven. The temperature was raised to 150° C. at a rate of 20° C./h and kept for 24 h, then reduced to 100° C. at a rate of 2° C./day and then reduced to 30° C. at a rate of 2° C./h, and the hydrothermal reactor was opened to obtain the NH4B4O6F crystal with a size of 5 mm×6 mm×8 mm.
The compound NH4B4O6F was synthesized according to the specific operation steps in Example 2 based on the reaction equation NH4F+2B2O3→NH4B4O6F.
The resultant compound NH4B4O6F was placed at the bottom of a hydrothermal reactor having a volume of 100 mL and lined with stainless steel with a platinum sleeve, and the hydrothermal reactor was placed into a muffle furnace. The temperature was raised to 300° C. at a rate of 30° C./h and kept for 15 h and then reduced to 30° C. at a rate of 2° C./h, and the hydrothermal reactor was opened to obtain a seed crystal of NH4B4O6F.
The resultant seed crystal was placed at the bottom of a hydrothermal reactor lined with stainless steel with a platinum sleeve, and then the resultant compound NH4B4O6F were placed into the hydrothermal reactor lined with stainless steel with the platinum sleeve.
The solvent of 50 mL deionized water was added to the hydrothermal reactor lined with stainless steel with the platinum sleeve. The hydrothermal reactor was screwed tightly to be sealed and then was placed into a muffle furnace. The temperature was raised to 250° C. at a rate of 30° C./h and kept for 24 h, then reduced to 200° C. at a rate of 2° C./day and then reduced to 30° C. at a rate of 5° C./h, and the hydrothermal reactor was opened to obtain the NH4B4O6F crystal with a size of 5 mm×6 mm×8 mm.
The compound NH4B4O6F was synthesized according to the specific operation steps in Example 2 based on the reaction equation NH4F+4H3BO3→NH4B4O6F+6H2O↑.
The resultant compound NH4B4O6F was placed at the bottom of a hydrothermal reactor having a volume of 150 mL and lined with stainless steel with a platinum sleeve, and the hydrothermal reactor was placed into a muffle furnace. The temperature was raised to 500° C. at a rate of 35° C./h and kept for 48 h and then reduced to 30° C. at a rate of 4° C./h, and the hydrothermal reactor was opened to obtain a seed crystal of NH4B4O6F.
The resultant seed crystal was placed at the bottom of a hydrothermal reactor lined with stainless steel with a platinum sleeve, and then the resultant compound NH4B4O6F were placed into the hydrothermal reactor lined with stainless steel with the platinum sleeve.
The solvent of 80 mL hydrofluoric acid was added to the hydrothermal reactor lined with stainless steel with the platinum sleeve. The hydrothermal reactor was screwed tightly to be sealed and then was placed into a muffle furnace. The temperature was raised to 600° C. at a rate of 40° C./h and kept for 48 h, then reduced to 550° C. at a rate of 3° C./day and then reduced to 30° C. at a rate of 10° C./h, and the hydrothermal reactor was opened to obtain the NH4B4O6F crystal with a size of 5 mm×6 mm×8 mm.
The compound NH4B4O6F was synthesized according to the specific operation steps in Example 2 based on the reaction equation NH4F+4H3BO3→NH4B4O6F+6H2O↑.
The resultant compound NH4B4O6F was placed at the bottom of the polytetrafluoroethylene lining of a hydrothermal reactor having a volume of 23 mL, and the hydrothermal reactor was placed into a drying oven. The temperature was raised to 220° C. at a rate of 40° C./h and kept for 48 h and then reduced to 30° C. at a rate of 5° C./h, and the hydrothermal reactor was opened to obtain a seed crystal of NH4B4O6F.
The resultant seed crystal was placed at the bottom of the polytetrafluoroethylene lining of a hydrothermal reactor, and then the resultant compound NH4B4O6F was placed into the polytetrafluoroethylene lining of the hydrothermal reactor.
The solvent of 10 mL N,N-dimethylacetamide was added to the polytetrafluoroethylene lining of the hydrothermal reactor. The hydrothermal reactor was screwed tightly to be sealed and then was placed into a drying oven. The temperature was raised to 210° C. at a rate of 40° C./h and kept for 35 h, then reduced to 160° C. at a rate of 3° C./day and then reduced to 30° C. at a rate of 4° C./h, and the hydrothermal reactor was opened to obtain the NH4B4O6F crystal with a size of 5 mm×6 mm×8 mm.
The NH4B4O6F crystal obtained in any one of Examples 1-24 was processed in the direction of phase matching, and placed in position 3 as shown in
The NH4B4O6F crystal obtained in any one of Examples 1-24 was processed in the direction of phase matching, and placed in position 3 as shown in
The NH4B4O6F crystal obtained in any one of Examples 1-24 was processed in the direction of phase matching, and placed in position 3 as shown in
| Number | Date | Country | Kind |
|---|---|---|---|
| 2016 1 1128283 | Dec 2016 | CN | national |
| Filing Document | Filing Date | Country | Kind |
|---|---|---|---|
| PCT/CN2017/074336 | 2/22/2017 | WO | 00 |
| Publishing Document | Publishing Date | Country | Kind |
|---|---|---|---|
| WO2018/103201 | 6/14/2018 | WO | A |
| Number | Name | Date | Kind |
|---|---|---|---|
| 9715160 | Pan | Jul 2017 | B2 |
| 10564514 | Pan | Feb 2020 | B1 |
| Number | Date | Country |
|---|---|---|
| 101984149 | Mar 2011 | CN |
| 102650075 | Aug 2012 | CN |
| 103031601 | Apr 2013 | CN |
| 103590106 | Feb 2014 | CN |
| Entry |
|---|
| Guoqiang Shi, Ying Wang, Fangfang Zhang, Bingbing Zhang, Zhihua Yang, Xueling Hou, Shilie Pan, and Kenneth R. Poeppelmeier. “Finding the Next Deep-Ultraviolet Nonlinear Optical Material: NH4B4O6F.” Journal of the American Chemical Society, 2017, vol. 139 (31), pp. 10645-10648. (Year: 2017). |
