CN-122013321-A - Sodium magnesium zinc hydroxy carbonate ultraviolet nonlinear optical crystal, preparation method and application

Abstract

The invention relates to a sodium magnesium zinc hydroxycarbonate ultraviolet nonlinear optical crystal, a preparation method and application thereof, wherein the chemical formula of the crystal is Na 2 Mg 0.34 Zn 0.66 C 2 O 7 H 2 , the crystal belongs to a tetragonal system, a space group is P-4 (No. 81), the crystal belongs to a non-heart space group, the unit cell parameters are a= 7.4555 (2) a, b= 7.4555 (2) a, c= 5.7592 (3) a, alpha=beta=gamma=90 DEG, Z=2, and unit cell volume V= 320.12 (2) a 3 . The sodium magnesium zinc hydroxycarbonate ultraviolet nonlinear optical crystal provided by the invention has a wide band gap of 5.65 eV, corresponds to an ultraviolet cut-off edge of 219.64nm, has a double refractive index of about 0.055 at 248nm and good phase matching capability in an ultraviolet region, has a theoretical frequency multiplication coefficient which is more than 2 times that of a KDP crystal, and has good mechanical properties, and is stable in air and not easy to deliquesce. Meanwhile, the crystal has simple preparation process, low cost and environment-friendly raw materials, has good application potential in the aspects of preparing a laser harmonic generator, an optical parametric amplifier and an optical waveguide device, and can realize the output of deep ultraviolet laser with the wavelength smaller than 400 nm.

Inventors

• Tang changcheng
• WU ZIJIN
• LI QING
• YANG CHAO
• LIU WANXING
• ZHOU DAKUN
• ZHAO WEN
• FENG JINGLIN
• ZHOU ZEYU
• ZHOU YAN
• Zhuo Yuwei
• HUANG YONGMING

Assignees

• 武夷学院

Dates

Publication Date

20260512

Application Date

20260213

Claims (6)

1. 1. The ultraviolet nonlinear optical crystal of sodium magnesium zinc hydroxycarbonate is characterized by having a chemical formula of Na 2 Mg 0.34 Zn 0.66 C 2 O 7 H 2 , belonging to tetragonal system, a space group of P-4 (NO. 81) and a non-cardiac space group, wherein the unit cell parameters of the crystal are a= 7.4555 (2) a, b= 7.4555 (2) a, c= 5.7592 (3) a, a=beta=gamma=90 DEG, Z=2, and unit cell volume V= 320.12 (2) a 3 .
2. 2. The method for preparing the sodium magnesium zinc hydroxycarbonate ultraviolet nonlinear optical crystal according to claim 1, wherein the crystal is prepared by a hydrothermal method, and the specific operation is carried out according to the following steps: a. Weighing raw materials according to the molar ratio of (0.5-1): (0.5-2): (1-2) of a magnesium-containing compound, a zinc-containing compound and a sodium-containing compound in an air condition, putting the raw materials into a polytetrafluoroethylene lining, adding 5-10 milliliters of deionized water or purified water, covering the lining, and putting the lining into a 304 stainless steel shell of a hydrothermal kettle for screwing, wherein the magnesium-containing compound is at least one of MgF 2 、MgO、Mg(OH) 2 、MgCO 3 , the zinc-containing compound is at least one of ZnCl 2 、ZnO、Zn(OH) 2 、Zn(NO 3 ) 2 6H 2 O, and the sodium-containing compound is at least one of Na 2 CO 3 、NaHCO 3 ; b. c, placing the hydrothermal kettle in the step a into a step temperature-controlled blast drying oven, heating to 240 ℃ at 0.5 ℃ per min, preserving heat for 24 hours, then cooling to 220 ℃ and preserving heat for 24 hours, then cooling to 180 ℃ and preserving heat for 24 hours, and finally cooling to room temperature; c. And opening the polytetrafluoroethylene lining, flushing the product with deionized water, and drying the cleaned crystal product in a drying oven to obtain the sodium magnesium zinc hydroxycarbonate ultraviolet nonlinear optical crystal.
3. 3. The sodium magnesium zinc hydroxycarbonate ultraviolet nonlinear optical crystal according to claim 1 is used for preparing harmonic generators, optical parametric oscillation and optical parametric amplification devices and optical waveguide devices in the ultraviolet region.
4. 4. Use of a sodium magnesium zinc hydroxycarbonate ultraviolet nonlinear optical crystal according to claim 1 for producing a harmonic output of shortest wavelength 219.64 nm.
5. 5. The use of a sodium magnesium zinc hydroxycarbonate ultraviolet nonlinear optical crystal according to claim 1, wherein the ultraviolet nonlinear optical crystal is used for preparing a harmonic generator in an ultraviolet region, an optical parametric oscillation and optical parametric amplification device and an optical waveguide device.
6. 6. The application of the sodium-magnesium-zinc hydroxycarbonate ultraviolet nonlinear optical crystal in the technical field of laser comprises the application of preparing an ultraviolet band laser variable frequency crystal, an ultraviolet laser, an ultraviolet optical device, an ultraviolet communication device, laser medical treatment, an ultraviolet lithography device and an ultraviolet micro-nano processing device.

Description

Sodium magnesium zinc hydroxy carbonate ultraviolet nonlinear optical crystal, preparation method and application Technical Field The invention relates to the technical field of nonlinear optical crystals. More particularly, it relates to a carbonate nonlinear optical crystal with a molecular formula of Na 2Mg0.34Zn0.66C2O7H2, a preparation method and application thereof. Background The ultraviolet nonlinear optical crystal refers to a crystal capable of outputting ultraviolet laser with the wavelength of 200-400 nm by changing the frequency of incident light through nonlinear optical effect. The crystal has important application value in the front-edge fields of optical communication, laser processing, optical sensing, quantum optics and the like. The nonlinear optical crystal is suitable for ultraviolet band, and at least meets three basic conditions, namely a first band gap reaching more than 3.1eV, a second nonlinear optical coefficient not lower than 2 times of potassium dihydrogen phosphate crystal (KDP), and a third moderate double refractive index (delta n) to realize phase matching. At present, most of the existing ultraviolet nonlinear optical crystals still have defects in the aspects of environmental stability, thermal stability, water resistance and the like, and are difficult to completely meet the actual application demands, so that the materials are restricted from further development and application in the technical field of laser to a certain extent. The sodium magnesium zinc hydroxycarbonate ultraviolet nonlinear optical crystal provided by the invention has a wide band gap of 5.65 eV, corresponds to an ultraviolet cut-off edge of 219.64nm, has a double refractive index of about 0.055 at 248nm and good phase matching capability in an ultraviolet region, has a theoretical frequency multiplication coefficient which is more than 2 times that of a KDP crystal, and has good mechanical properties, and is stable in air and not easy to deliquesce. Meanwhile, the crystal has the advantages of simple preparation process, low cost, environment-friendly raw materials and good application potential. Disclosure of Invention The invention aims to provide a sodium magnesium zinc hydroxycarbonate ultraviolet nonlinear optical crystal. The invention further aims at providing a preparation method of the sodium magnesium zinc hydroxycarbonate ultraviolet nonlinear optical crystal. It is still another object of the present invention to provide the use of a sodium magnesium zinc hydroxycarbonate ultraviolet nonlinear optical crystal. The sodium magnesium zinc hydroxycarbonate ultraviolet nonlinear optical crystal has a chemical formula of Na 2Mg0.34Zn0.66C2O7H2, belongs to a tetragonal system, belongs to a space group of P-4 (No. 81), belongs to a non-cardiac space group, and has unit cell parameters of a= 7.4555 (2) a, b= 7.4555 (2) a, c= 5.7592 (3) a, a=beta=gamma=90°, Z=2, and a unit cell volume of V= 320.12 (2) a 3. The method for growing the sodium magnesium zinc hydroxycarbonate ultraviolet nonlinear optical crystal by the hydrothermal method comprises the following steps of: a. Weighing raw materials according to the molar ratio of (0.5-2) to (1-2) of magnesium element, zinc element and sodium element, putting the raw materials into a polytetrafluoroethylene lining under the air condition, adding 5-10 milliliters of deionized water or purified water, covering the lining, and putting the lining into a 304 stainless steel shell of a hydrothermal kettle for screwing, wherein the magnesium compound is at least one of MgF 2、MgO、Mg(OH)2、MgCO3, the zinc compound is at least one of ZnCl 2、ZnO、Zn(OH)2、Zn(NO3)26H2 O, and the sodium compound is at least one of Na 2CO3、NaHCO3; b. C, placing the hydrothermal kettle in the step a into a step temperature-controlled blast drying oven, heating to 240 ℃ at 0.5 ℃ per min, preserving heat for 24 hours, then cooling to 220 ℃ and preserving heat for 24 hours, then cooling to 180 ℃ and preserving heat for 24 hours, and finally cooling to room temperature; c. And opening the polytetrafluoroethylene lining, flushing the product with deionized water, and drying the cleaned crystal product in a drying oven to obtain the sodium magnesium zinc hydroxycarbonate ultraviolet nonlinear optical crystal. Preferably, the molar ratio of magnesium element, zinc element, sodium element in the magnesium-containing compound, zinc-containing compound, sodium-containing compound can also be, but is not limited to, 1:0.5:1, 1:0.5:1.5, 1:0.5:2, 1:1:1, 1:1:1.5, 1:1:2, 1:1.5:1.5:1.5, 1:1.5:2, 1:2:1, 1:2:1.5, 1:2:2:2. The sodium magnesium zinc hydroxycarbonate ultraviolet nonlinear optical crystal is used for frequency conversion of laser output of a laser. Use of the sodium magnesium zinc hydroxycarbonate ultraviolet nonlinear optical crystal for producing a harmonic output of the shortest wavelength 219.64 nm. The sodium magnesium zinc hydroxycarbonate ultraviolet nonlinear optical crystal is used