CN-117624196-B - Series compound methyltrifluoroborate and methyltrifluoroborate nonlinear optical crystal, preparation method and application thereof

Abstract

The invention relates to a series of compounds methyl trifluoro borate and a nonlinear optical crystal of the methyl trifluoro borate and a preparation method and application thereof, wherein the molecular general formula of the series of compounds is A 3 [CH 3 BF 3 ]X 2 , wherein A=NH 4 ,K,Rb,Cs,X=[NO 3 , cl and Br, the molecular weight is 207.86-641.37, the series of compounds are prepared by adopting a top seed crystal method, an orthorhombic crystal system and a space group Cmc2 1 (No. 36), and the nonlinear optical crystal of the series of compounds methyl trifluoro borate, which is obtained by the method, has the advantages of wider light transmission wave band, stable physical and chemical properties, moderate mechanical hardness, difficult fragmentation, easy cutting, polishing processing and preservation, and the like.

Inventors

• PAN SHILIE
• QIU HAOTIAN
• Mizhidin Mutalip

Assignees

• 中国科学院新疆理化技术研究所

Dates

Publication Date

20260508

Application Date

20231120

Claims (3)

1. 1. A series of nonlinear optical crystals of methyltrifluoroborate is characterized by the molecular general formula A 3 [CH 3 BF 3 ]X 2 , wherein A=NH 4 ,K,Rb,Cs,X = [NO 3 , cl, br, no symmetry center, orthorhombic system, space group Cmc2 1 (No. 36), unit cell parameters ：1） (NH 4 ) 3 [CH 3 BF 3 ][NO 3 ] 2 ：a = 11.8272(14) Å,b = 8.1556 (12) Å,c = 10.9621(9) Å,α=90,β=90,γ=90,Z = 4,V= 925.609(2)Å 3 ; 2）K 3 [CH 3 BF 3 ][NO 3 ] 2 ：a = 11.9141(17) Å,b = 8.1556(12) Å,c = 10.9621(14) Å,α=90,β=90,γ=90,Z = 4,V= 1065.2(3)Å 3 ; 3）Rb 3 [CH 3 BF 3 ][NO 3 ] 2 ：a = 12.0141(10) Å,b = 8.3542(10) Å,c = 11.3254(2) Å,α=90,β=90,γ=90,Z = 4,V= 1135.27 (4)Å 3 ; 4）Cs 3 [CH 3 BF 3 ][NO 3 ] 2 ：a = 12.210(4) Å,b = 8.417(4) Å,c = 11.5247(8) Å,α=90,β=90,γ=90,Z = 4,V= 1178.52(15) Å 3 ; 5） (NH 4 ) 3 [CH 3 BF 3 ]Cl 2 ：a = 12.0246(14) Å,b = 8.2314(12) Å,c = 11.3654 (9) Å,α=90,β=90,γ=90,Z = 4,V= 1124.4(2)Å 3 ; 6） K 3 [CH 3 BF 3 ]Cl 2 ：a = 12.2214(14) Å,b = 8.2503(12) Å,c = 11.3324 (9) Å,α=90,β=90,γ=90,Z = 4,V= 1142.2(2)Å 3 ; 7）Rb 3 [CH 3 BF 3 ]Cl 2 ：a = 12.4265(15) Å,b = 8.3310(12) Å,c = 11.4513 (9) Å,α=90,β=90,γ=90,Z = 4,V= 1185.3(6)Å 3 ; 8）Cs 3 [CH 3 BF 3 ]Cl 2 ：a = 12.3327(15) Å,b = 8.3945(17) Å,c = 11.5041(7) Å,α=90,β=90,γ=90,Z = 4,V= 1191.1(3)Å 3 ; 9） (NH 4 ) 3 [CH 3 BF 3 ]Br 2 ：a = 12.0246(14) Å,b = 8.2314(12) Å,c = 11.3654 (9) Å,α=90,β=90,γ=90,Z = 4,V= 1124.4(2)Å 3 ; 10） K 3 [CH 3 BF 3 ]Br 2 ：a = 12.2463(6) Å,b = 8.4654(17) Å,c = 11.5205 (9) Å,α=90,β=90,γ=90,Z = 4,V= 1195.3(7)Å 3 ;11） Rb 3 [CH 3 BF 3 ]Br 2 ：a = 12.2463(6) Å,b = 8.4654(17) Å,c = 11.5205 (9) Å,α=90,β=90,γ=90,Z = 4,V= 1195.3(7)Å 3 ; 12） Cs 3 [CH 3 BF 3 ]Br 2 ：a = 12.6254(2) Å,b = 8.2716(4) Å,c = 11.5625(15) Å,α=90,β=90,γ=90,Z = 4,V= 1207.44(7) Å 3 .
2. 2. The preparation method of the series of methyltrifluoroborate nonlinear optical crystals as claimed in claim 1, wherein the preparation method is characterized by adopting a top seed crystal method, and the specific operation is carried out according to the following steps: a. Uniformly mixing a fluorine-containing compound and methyl boric acid according to the molar ratio of 1.5-3.5:1, adding 0-50 mL deionized water to fully mix and dissolve the mixture to obtain a mixed solution, wherein the fluorine-containing compound is ammonium bifluoride, potassium bifluoride, rubidium bifluoride, cesium bifluoride, ammonium tetrafluoroborate, potassium tetrafluoroborate, rubidium tetrafluoroborate or cesium tetrafluoroborate; b. Standing the mixed solution in the step a for 2-5 days at constant temperature, taking out the crystal when the solvent is volatilized to supersaturation and starts to precipitate the crystal, and airing the crystal on filter paper when the solvent is not volatilized completely to obtain a series of compounds containing methyl trifluoro ammonium borate, potassium methyl trifluoro borate, rubidium methyl trifluoro borate or cesium methyl trifluoro borate; c. Mixing the methyl trifluoro boric acid compound obtained in the step b with nitric acid or halogen compound according to the mol ratio of 1:1.8-2, grinding uniformly, adding 50-150 mL deionized water to make them fully mixed and dissolved to obtain mixed liquor, wherein the nitric acid or halogen compound is ammonium nitrate, potassium nitrate, rubidium nitrate, cesium nitrate, ammonium chloride, potassium chloride, rubidium chloride, cesium chloride, ammonium bromide, potassium bromide, rubidium bromide or cesium bromide; Or directly mixing fluorine-containing compound, methyl boric acid and nitric acid or halogen-containing compound uniformly according to the mol ratio of 1.5-2.5:1:2.5-4 to obtain a mixture, and adding 50-100ml deionized water to fully dissolve the mixture to obtain a mixed solution; d. C, preparing the series of A 3 [CH 3 BF 3 ]X 2 seed crystals, namely keeping the mixed solution in the step c at constant temperature for 2-5 days, standing in a polytetrafluoroethylene beaker, sealing with a polyvinyl chloride film, placing in a static environment without shaking, pollution and air convection, pricking a plurality of small holes in the seal to adjust the volatilization rate of a solvent in the solution, starting to precipitate crystals after the solution is saturated, and taking out the crystals with better quality to obtain the series of compound A 3 [CH 3 BF 3 ]X 2 seed crystals; e. And d, fixing the seed crystal obtained in the step d on a seed rod, seeding the seed crystal from the top of the water solution crystal growth furnace, lowering the seed crystal to the surface of the saturated mixed solution contacted with the step d, heating the seed crystal to 45-50 ℃, rotating the seed rod at a rotating speed of 1-60rpm for crystal growth, keeping the temperature for 1-3 days, cooling the seed crystal to room temperature at a cooling rate of 0.5 ℃ per hour, and taking the seed crystal out of the solution to obtain the series A 3 [CH 3 BF 3 ]X 2 nonlinear optical crystals.
3. 3. Use of a series of methyltrifluoroborate nonlinear optical crystals according to claim 1 for preparing harmonic light output of frequency multiplication 2 of fundamental frequency light 1064 nm output by a nd:yag laser.

Description

Series compound methyltrifluoroborate and methyltrifluoroborate nonlinear optical crystal, preparation method and application thereof Technical Field The invention relates to a series of compounds methyl trifluoro borate and a nonlinear optical crystal of the methyl trifluoro borate, a preparation method and application thereof. Background The ultraviolet nonlinear optical material is a key material for generating ultraviolet coherent light by a solid-state laser, and in order to obtain the nonlinear optical material with nonlinear optical properties, a method which is commonly used internationally at present is to introduce nonlinear optical functional elements which are easy to distort into a structure, wherein the elements mainly comprise transition metal cation polyhedrons containing d 0,d10 electron structures or metal cation polyhedrons containing lone electron pairs. However, these structural elements often red shift the UV cut-off edge of the material, making it unusable in the UV region. Borates, in turn, are characterized by favoring the transmission of ultraviolet radiation, and many excellent nonlinear optical crystals have been found in borates, such as BBO (. Beta. -BBO), LBO (LiB 3O5) crystals, CBO (CsB 3O5) crystals, CLBO (CsLiB 6O10) crystals, and KBBF (KBe 2BO3F2) crystals. Although the crystal growth techniques of these materials have been mature, there are significant disadvantages such as deliquescence of the crystals, long growth period, severe habit of lamellar growth, and high price. Thus, the synthesis of new nonlinear optical crystal materials remains a very important and arduous task. When developing new ultraviolet nonlinear optical crystal, people still select borate crystal with wide light transmission range and large laser damage threshold value, and in order to further widen the light transmission range, the ultraviolet cut-off edge of the borate crystal can reach deep ultraviolet, the cation generally uses alkali metal or alkaline earth metal without d-d electron transition, and fluoride ions are introduced into borate skeleton. Disclosure of Invention The invention aims to provide a series of compounds, namely methyltrifluoroborate, which has a molecular general formula of A3[ CH3BF3] X2, wherein A=NH 4, K, rb and Cs, and has a molecular weight of 162.88-277.75, and the compounds are prepared by a top seed crystal method. It is another object of the present invention to provide a series of compounds methyltrifluoroborate a 3[CH3BF3]X2 nonlinear optical crystals, wherein a=nh 4,K,Rb,Cs,X＝[NO3 ], cl, br, having no symmetry center, orthorhombic system, space group Cmc2 1 (No. 36), unit cell parameters: 1) (NH 4)3[CH3BF3][NO3]2:α=90,β=90,γ=90,Z=4,2)K3[CH3BF3][NO3]2:α=90,β=90,γ=90,Z=4,3)Rb3[CH3BF3][NO3]2:α=90,β=90,γ=90,Z=4,4)Cs3[CH3BF3][NO3]2:α=90,β=90,γ=90,Z=4,5)(NH4)3[CH3BF3]Cl2:α=90,β=90,γ=90,Z=4,6)K3[CH3BF3]Cl2:α=90,β=90,γ=90,Z=4,7)Rb3[CH3BF3]Cl2:α=90,β=90,γ=90,Z=4,8)Cs3[CH3BF3]Cl2:α=90,β=90,γ=90,Z=4,9)(NH4)3[CH3BF3]Br2:α=90,β=90,γ=90,Z=4,10)K3[CH3BF3]Br2:α=90,β=90,γ=90,Z=4,11)Rb3[CH3BF3]Br2:α=90,β=90,γ=90,Z=4,11)Cs3[CH3BF3]Br2:α=90,β=90,γ=90,Z=4, it is still another object of the present invention to provide a method for preparing a series of methyltrifluoroborate nonlinear optical crystals using a top-seeded process to grow the crystals. It is a further object of the present invention to provide the use of the series of methyltrifluoroborate a 3[CH3BF3]X2 nonlinear optical crystals. The molecular general formula of the series of compounds is A 3[CH3BF3]X2, wherein A=NH 4,K,Rb,Cs,X＝[NO3, cl and Br, the molecular weight is 207.86-641.37, and the series of compounds are prepared by a top seed crystal method. A series of methyltrifluoroborate nonlinear optical crystals having the molecular formula a 3[CH3BF3]X2, wherein a=nh 4,K,Rb,Cs,X＝[NO3, cl, br, having no symmetry center, orthorhombic system, space group Cmc2 1 (No. 36), unit cell parameters: 1) (NH 4)3[CH3BF3][NO3]2:α=90,β=90,γ=90,Z=4,2)K3[CH3BF3][NO3]2:α=90,β=90,γ=90,Z=4,3)Rb3[CH3BF3][NO3]2:α=90, β=90,γ=90,Z=4,4)Cs3[CH3BF3][NO3]2: α=90,β=90,γ=90,Z=4,5)(NH4)3[CH3BF3]Cl2:α=90,β=90,γ=90,Z=4,6)K3[CH3BF3]Cl2:α=90,β=90,γ=90,Z=4,7)Rb3[CH3BF3]Cl2:α=90,β=90,γ=90,Z=4,8)Cs3[CH3BF3]Cl2:α=90,β=90,γ=90,Z=4,9)(NH4)3[CH3BF3]Br2:α=90,β=90,γ=90,Z=4,10)K3[CH3BF3]Br2:α=90,β=90,γ=90,Z=4,11)Rb3[CH3BF3]Br2:α=90,β=90,γ=90,Z=4,11)Cs3[CH3BF3]Br2:α=90,β=90,γ=90,Z=4, the preparation method of the series of methyl trifluoro borate nonlinear optical crystals adopts a top seed crystal method, and comprises the following specific operations: a. Uniformly mixing a fluorine-containing compound and methyl boric acid according to the molar ratio of 1.5-3.5:1, adding 0-50mL of deionized water to fully mix and dissolve the mixture, and obtaining a mixed solution, wherein the fluorine-containing compound is ammonium bifluoride, potassium bifluoride, rubidium bifluoride, cesium bifluoride, ammonium tetrafluoroborate, potassium tetrafluoroborate, rubidium tetr