CN112410877B - Zirconium-cesium fluoroiodate second-order nonlinear optical crystal and preparation and application thereof - Google Patents
Zirconium-cesium fluoroiodate second-order nonlinear optical crystal and preparation and application thereof Download PDFInfo
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Abstract
The invention relates to a zirconium cesium fluoroiodate second-order nonlinear optical crystal and preparation and application thereof, wherein the chemical formula of the crystal material is CsZrF4(IO3) Molecular weight of 475.03, belonging to the orthorhombic system, space group Ima2, unit cell parameter
α ═ β ═ γ ═ 90 °, Z ═ 4, and unit cell volume
The zirconium cesium fluoroiodate crystal material has excellent optical performance, the powder frequency doubling intensity is about 4.5 times of that of a monopotassium phosphate crystal under 1064nm laser irradiation, and the laser damage threshold value of the crystal material measured under the laser with the wavelength of 1064nm is 68 times of that of a commercialized infrared second-order nonlinear material silver gallium sulfur. In addition, the crystal material has a wide transmission range in an ultraviolet-visible light-infrared light region (0.3-8 mu m), and has wide application prospects in the fields of laser frequency conversion, photoelectric modulation, laser signal holographic storage and the like.
Description
Technical Field
The invention belongs to the technical field of optical crystal materials, and relates to a zirconium cesium fluoroiodate second-order nonlinear optical crystal and preparation and application thereof.
Background
The second-order nonlinear optical crystal is a photoelectric functional material widely applied to the laser field, and has important application values in the aspects of laser frequency conversion, photoelectric modulation, laser signal holographic storage, laser communication and the like. The second-order nonlinear optical material which is practically used at present is beta-barium metaborate (beta-BaB)2O4) Lithium borate (LiB)3O5) Potassium dihydrogen phosphate (KH)2PO4) Potassium titanyl phosphate (KTiOPO)4) Lithium niobate (LiNbO)3) Barium titanate (BaTiO)3) Silver gallium sulfur (AgGaS)2) Zinc germanium phosphorus (ZnGeP)2) And the nonlinear optical material applied to the infrared band has defects in properties, so that the elbow is usually applied in practical application. 3-5 μm and 8-12 μm bands in infrared region as atmospheric transmission window, and intermediate infrared nonlinear optical material suitable for the bandsThe method has wide application prospect in civil fields such as laser guidance, infrared remote sensing, medical diagnosis and treatment, laser communication, industrial control and the like; meanwhile, recently, the application demand of the laser in the band in the technical fields of military affairs, such as target tracking and positioning, infrared countermeasure, and the like, is rapidly increased. With the wide application of infrared laser technology and the rapid development of nonlinear optical devices, the current requirements for the physical and chemical properties of infrared nonlinear optical materials are higher and higher, and the current commercialized infrared nonlinear optical crystal materials cannot meet the requirements of practical application. Therefore, the research on novel nonlinear optical crystal materials applicable to the middle infrared is an important direction in the field of current inorganic optical functional materials.
In recent years, metal iodate has attracted extensive attention in the field of inorganic nonlinear optical crystal materials due to its excellent properties, such as stronger frequency doubling effect, wider transmission band, higher laser damage threshold, thermal stability and the like, and is a kind of nonlinear optical crystal material expected to be practically applied, but no literature report of such infrared nonlinear optical crystal material which can be practically applied is found at present.
Disclosure of Invention
The invention aims to provide a zirconium cesium fluoroiodate second-order nonlinear optical crystal, and preparation and application thereof, so as to obtain a crystal material with both large band gap and strong nonlinear optical performance, and the crystal material has extremely high laser damage threshold and wide infrared transmission range.
The purpose of the invention can be realized by the following technical scheme:
in one aspect, the invention provides a zirconium cesium fluoroiodate second-order nonlinear optical crystal with a chemical formula of CsZrF4(IO3)。
Further, the optical crystal belongs to the orthorhombic system, the space group is Ima2, and the unit cell parameter is
α ═ β ═ γ ═ 90 °, Z ═ 4, and unit cell volume
The crystal structure of the zirconium cesium fluoroiodate of the invention is as follows: each Zr4+Ions are respectively coordinated with two oxygen atoms and six fluorine atoms to form cis-ZrO2F6Polyhedra in which two oxygen ligands are respectively associated with two different IOs3The groups are connected to further form cis-form [ ZrF6(IO3)2]4-A polyanion; between adjacent polyanions by ZrO2F6The common edges of the polyhedrons are mutually connected to form a one-dimensional anion long chain extending along the c-axis direction; the one-dimensional long-chain structures are connected through Cs-O/F bonds to form a three-dimensional network structure.
On the other hand, the invention also provides a preparation method of the zirconium cesium oxyfluoride second-order nonlinear optical crystal, which comprises the steps of firstly mixing a zirconium source, a cesium source, an iodine source, a fluorine source, nitric acid and water to obtain an initial mixture, and then crystallizing under a hydrothermal condition to obtain a target product.
Further, in the initial mixture, the ratio of zirconium element, cesium element, iodine element, fluorine element, nitric acid and water is 1mmol: (0.5-20) mmol: (0.5-50) mmol: (1-50) mmol: (0-4) mL: (0.5-10) mL. Preferably, the molar ratio of the zirconium element, the cesium element, the iodine element, the fluorine element, the nitric acid and the water is 1mmol: (1-10) mmol: (1-15) mmol: (2-20) mmol: (0.1-2) mL: (1-5) mL. The mass concentration of the nitric acid is about 64-68% generally.
Further, the zirconium source is zirconium nitrate, zirconyl nitrate, zirconium oxide or zirconium hydroxide; preferably, the zirconium source is zirconium nitrate.
Further, the cesium source is cesium fluoride, cesium carbonate or cesium nitrate; preferably, the cesium source is cesium fluoride.
Further, the iodine source is diiodo pentaoxide, iodic acid or periodic acid; preferably, the iodine source is diiodo pentoxide.
Further, the fluorine source is cesium fluoride or hydrofluoric acid; preferably, the fluorine source is cesium fluoride.
Furthermore, the temperature of the hydrothermal condition is 150-230 ℃, and the crystallization time is not less than 24 h. Preferably, the hydrothermal condition temperature is 180-220 ℃, and the crystallization time is not less than 48 h.
Further, after crystallization is finished, the obtained product is cooled to room temperature at a cooling rate of 0.5-15 ℃/h, and then the product is filtered and cleaned to obtain the target product. Preferably, the cooling rate is 0.5-6 ℃/h.
Further, the crystallization process is carried out in a closed reaction kettle.
During crystallization, the anions in the zirconium source are replaced by fluoride and oxygen ions to form cis-ZrO2F4Polyhedral group, which is further associated with IO in iodine source3The groups are polymerized to form a cis [ ZrF ] of the oxygen linkage6(IO3)2]4-Polyanionic groups formed by polycondensation of fluoro ligands [ ZrF ]6(IO3)2]∞The one-dimensional chain structure, the cesium source provides cations to maintain the charge balance of the compound structure, and the nitric acid provides an acidic environment in the crystallization reaction and serves as a mineralizer to improve the crystal quality and the crystallization rate.
Because the raw materials of the cesium source and the iodine source have high solubility in water, in order to ensure that the amount of two ions in an aqueous solution reaches a precipitation concentration, the addition amount of the cesium source and the iodine source needs to be larger than the stoichiometric ratio of the molecular formula of the product, and the target product cannot be crystallized due to the fact that the addition amount of the cesium source and the iodine source is too low. The addition amount of the raw materials is not within the limited range of the invention, which can cause the yield of the target product to be reduced and the yield of the by-products to be increased, for example, when the zirconium source and the iodine source are excessive, the product is mainly Zr (IO)3)4And Cs2Zr(IO3)6(ii) a When the fluorine source is excessive, the main product is Cs2ZrF6. The crystallization temperature is defined on the premise that crystals of the target product can be formed, and the target crystals cannot be formed below or above the defined temperature range.
In yet another aspect, the invention also provides a methodThe application of the zirconium cesium oxyfluoride second-order nonlinear optical crystal is used for visible, middle and far infrared laser frequency conversion output. The zirconium cesium fluoroiodate crystal material has a large frequency doubling effect, and the powder frequency doubling effect is about KH under 1064nm laser irradiation2PO44.5 times of the crystal, and is type I phase matching. The laser damage threshold value is the commercialized infrared optical frequency doubling material AgGaS measured under the laser irradiation with the wavelength of 1064nm268 times of the crystal. In addition, the optical transmission range of the crystal material is 0.3-8 μm, and the thermal stability temperature is 430 ℃. Therefore, the crystal material has wide application prospect in the field of nonlinear optics.
Furthermore, the second-order nonlinear optical crystal is used for preparing a frequency doubling generator, an optical parametric oscillator, an optical parametric amplifier or a photoelectric rectifier.
Compared with the prior art, the invention has the following advantages:
(1) the invention provides a novel inorganic crystal material of zirconium cesium fluoroiodate, which has a larger frequency doubling effect and is about KH under 1064nm laser irradiation2PO4The I-type phase matching can be realized by 4.5 times of the frequency doubling intensity of the crystal. The laser damage threshold value of the laser measured under laser with the wavelength of 1064nm is the commercialized infrared optical frequency doubling material AgGaS268 times of the crystal. In addition, the crystal material has wide transmission ranges in an ultraviolet-visible light region and an infrared light region, a complete optical transmission waveband is 0.3-8 mu m, the thermal stability temperature reaches 430 ℃, and the crystal material has wide application prospects in the fields of laser frequency conversion, photoelectric modulation, laser signal holographic storage and the like;
(2) the invention provides a preparation method of a zirconium cesium oxyfluoride crystal material, which adopts a hydrothermal method with mild reaction conditions, can obtain a high-purity crystalline sample at a high yield through hydrothermal crystallization at the temperature of 150-230 ℃, is simple, has mild conditions, and is beneficial to large-scale industrial production;
(3) the zirconium cesium oxyfluoride crystal material can be applied to a laser frequency converter and can be used for outputting visible and infrared laser beams in a frequency doubling harmonic wave mode.
Drawings
FIG. 1 is a schematic representation of the crystal structure of cesium zirconium oxyfluoride;
FIG. 2 is a comparison of X-ray diffraction patterns; wherein (a) is an X-ray diffraction pattern obtained by simulating a crystal structure analyzed by sample No. 1 according to single crystal X-ray diffraction data; (b) is a spectrum obtained by grinding a sample No. 1 into powder and then testing the powder by X-ray diffraction;
FIG. 3 is an ultraviolet-visible-near infrared absorption spectrum of sample # 1;
FIG. 4 is an IR spectrum (2.5 to 25 μm) of sample No. 1;
FIG. 5 is a thermogravimetric analysis plot of sample # 1;
FIG. 6 shows sample No. 1 and KH2PO4A second harmonic signal diagram with the sample size within the range of 105-150 mu m;
FIG. 7 is a graph of second harmonic phase matching for sample # 1 in the 1.064 μm band.
Detailed Description
The invention is described in detail below with reference to the figures and specific embodiments. The present embodiment is implemented on the premise of the technical solution of the present invention, and a detailed implementation manner and a specific operation process are given, but the scope of the present invention is not limited to the following embodiments.
In the following examples, the starting products or process techniques, if not specifically mentioned, are all conventional commercial products or conventional processing techniques in the art.
Example 1:
hydrothermal synthesis of samples
Mixing a zirconium source, a cesium source, an iodine source, a fluorine source, nitric acid or hydrofluoric acid and water according to a certain proportion to obtain initial raw materials, sealing the initial raw materials in a hydrothermal reaction kettle with a polytetrafluoroethylene lining, heating the initial raw materials to a crystallization temperature, keeping the temperature for a period of time, slowly cooling the temperature of a reaction system to room temperature at a certain rate, filtering and cleaning the reaction system to obtain colorless blocky cesium zirconium fluoiodate crystals.
The relationship between the type and ratio of raw materials in the initial mixture, crystallization temperature, crystallization time and sample number is shown in Table 1.
TABLE 1 correspondences between samples and starting materials and Synthesis conditions
Example 2
Crystal structure analysis
The structure of samples # 1 to # 6 was analyzed by single crystal X-ray diffraction and powder X-ray diffraction methods.
Wherein the single crystal X-ray diffraction test is carried out on a Bruker co D8 VENTURE CMOS X-ray single crystal diffractometer, germany. The crystal size is 0.22X 0.11X 0.05mm3(ii) a The data collection temperature is 293K, and the diffraction light source is Mo-Ka ray monochromized by graphite
The scanning mode is omega; the data were subjected to absorption correction processing using the Multi-Scan method. The structure analysis is completed by adopting a SHELXTL-97 program package; determining the position of heavy atom by direct method, and obtaining the coordinates of other atoms by difference Fourier synthesis method; with radicals based on F2The full matrix least square method refines the coordinates and anisotropic thermal parameters of all atoms.
Powder X-ray diffraction test was carried out on an X-ray powder diffractometer of Bruker D8 model, Bruker, Germany, under the conditions of a fixed target monochromatic light source Cu-Ka, wavelength
The voltage and current are 40kV/20A, the slit DivSlit/RecSlit/SctSlit is 2.00deg/0.3mm/2.00deg, the scanning range is 5-70 deg, and the scanning step is 0.02 deg.
Wherein, the single crystal X-ray diffraction test result shows that samples 1# to 6# have the same chemical structural formula and crystal structure, and the chemical formula is CsZrF4(IO3) Molecular weight of 475.03, belonging to the orthorhombic system, space group Ima2, unit cell parameter
α ═ β ═ γ ═ 90 °, Z ═ 4, and unit cell volume
Represented by sample # 1, whose crystal structure data is
α ═ β ═ γ ═ 90 °, Z ═ 4, and unit cell volume
The crystal structure is shown in figure 1, and CsZrF4(IO3) The size range of the crystal particles is about 0.5-1.5 mm.
The powder X-ray diffraction test result shows that the peak positions of the samples are basically the same and the peak intensities are slightly different on the XRD spectrograms of the samples 1# to 6 #.
Typically represented by sample # 1, as shown in FIG. 2. The pattern obtained by grinding the sample No. 1 in the figure 2(a) into powder and testing by X-ray diffraction is consistent with the X-ray diffraction pattern obtained by simulating the crystal structure analyzed according to the single crystal X-ray diffraction in the figure 2(b), and the peak position and the peak intensity are consistent, which indicates that the obtained sample has high purity.
Example 3
Ultraviolet diffuse reflectance spectroscopy test
The diffuse reflectance absorption spectroscopy test of sample # 1 was performed on an agilent Cary 5000 model uv-vis-nir spectrophotometer, usa. As shown in FIG. 3, it can be seen from FIG. 3 that the compound does not absorb significantly in the range of 300nm to 2500 nm. The compound has a wide optical transmission range and an optical band gap of 4.10 eV.
Example 4
Infrared Spectrum testing
The infrared spectroscopy test of sample # 1 was performed on a Nicolet iS10 model fourier infrared spectrometer, zemer feishol technologies ltd. As shown in FIG. 4, it can be seen from FIG. 4 that the compound has no significant absorption in the range of 2.5 to 8 μm and has a wide optical transmission range.
Example 5
Thermogravimetric testing
The thermogravimetric test of sample # 1 was carried out on a thermogravimetric analyzer model Netzsch STA 409PC, a company name of manufacture of equipment resistant to relaxation, germany. As shown in FIG. 5, it can be seen from FIG. 5 that the compound was stable to 430 ℃ and had good thermal stability.
Example 6
Frequency doubling test experiment and results
The frequency doubling test experiment of sample # 1 is as follows: YAG solid laser with 1064nm wavelength is used as fundamental frequency light to irradiate the tested crystal powder, the photomultiplier is used to detect the generated second harmonic, and oscilloscope is used to display the harmonic intensity. The crystal sample and the control sample KH are mixed2PO4And respectively grinding the crystals, and screening out the crystals with different granularity by using a standard screen, wherein the granularity ranges from less than 26, 26-50, 50-74, 74-105, 105-150, 150-200 and 200-280 mu m. And observing the trend of the intensity of the frequency multiplication signal along with the change of granularity, and judging whether the frequency multiplication signal can realize phase matching. Comparison of samples with KH under the same test conditions2PO4The strength of the second harmonic generated by the sample, and thus the relative magnitude of the frequency doubling effect of the sample.
Test results show that the compound zirconium cesium fluoroiodate crystal has a large frequency doubling effect, and the frequency doubling signal intensity is KH of a reference sample under the irradiation of laser with the wavelength of 1064nm2PO44.5 times of the crystal (as shown in FIG. 6), and I-type phase matching (as shown in FIG. 7) can be realized.
Example 7
Laser damage threshold test and results
The laser damage threshold test experiment of sample # 1 is as follows: aiming at a certain point of a crystal sample, adopting laser irradiation with the wavelength of 1064nm, the working frequency of 1Hz and the pulse width of 10ns, and adjusting the laser energy to gradually increase from 1-250 mJ until the point is damaged. The absolute value of the laser damage threshold of the sample can be calculated according to the laser energy and the laser spot area when the damage occurs.
Under the same test conditions, the zirconium cesium fluoroiodate crystal and AgGaS are measured2The laser damage threshold of the crystal is 142.2MW/cm2And 2.1MW/cm2The former is about 68 times as much as the latter.
Example 2:
a similar preparation method to that of example 1 was employed, except that:
the zirconium source is zirconium oxide, wherein the ratio of zirconium element, cesium element, iodine element, fluorine element, nitric acid and water in the initial mixture is 1mmol:3mmol:3mmol:3mmol:0.5mL:2 mL;
the crystallization temperature is 210 ℃ and the crystallization time is 60 hours.
Detecting to obtain CsZrF4(IO3) The crystal structure data of the sample is
α ═ β ═ γ ═ 90 °, Z ═ 4, and unit cell volume
The prepared CsZrF4(IO3) The crystal has a large frequency doubling effect, and the frequency doubling signal intensity is 4.5 times that of the KDP crystal under the laser irradiation with the wavelength of 1064 nm.
Example 3:
a similar preparation method to that of example 1 was employed, except that:
the cesium source is cesium nitrate, and the fluorine source is hydrofluoric acid, wherein the ratio of zirconium element, cesium element, iodine element, fluorine element, nitric acid and water in the initial mixture is 1:2:3:4:0.2mL:3 mL;
the crystallization temperature is 180 ℃ and the crystallization time is 80 hours.
Detecting to obtain CsZrF4(IO3) The crystal structure data of the sample is
α ═ β ═ γ ═ 90 °, Z ═ 4, and unit cell volume
The prepared CsZrF4(IO3) The crystal has a large frequency doubling effect, and the frequency doubling signal intensity is 4.5 times that of the KDP crystal under the laser irradiation with the wavelength of 1064 nm.
Example 4:
a similar preparation method to that of example 1 was employed, except that:
the iodine source is iodic acid, wherein the ratio of zirconium element, cesium element, iodine element, fluorine element, nitric acid and water in the initial mixture is 1:3:4:3:0.5mL:3 mL;
the crystallization temperature is 210 ℃ and the crystallization time is 70 hours.
Detecting to obtain CsZrF4(IO3) The crystal structure data of the sample is
α ═ β ═ γ ═ 90 °, Z ═ 4, and unit cell volume
The prepared CsZrF4(IO3) The crystal has a large frequency doubling effect, and the frequency doubling signal intensity is 4.5 times that of the KDP crystal under the laser irradiation with the wavelength of 1064 nm.
Comparative example 1:
compared with 1# in example 1, the method is mostly the same except that the addition of nitric acid as a raw material is omitted.
Detecting to obtain CsZrF4(IO3) Sample crystalThe structural data is
α ═ β ═ γ ═ 90 °, Z ═ 4, and unit cell volume
The prepared CsZrF4(IO3) The samples ranged in size from about 0.1 to about 0.3mm, with a significant reduction in crystal grain size compared to sample # 1 from example 1 (about 0.5 to about 1.5 mm).
The prepared CsZrF4(IO3) The crystal has a large frequency doubling effect, and the frequency doubling signal intensity is 4.5 times that of the KDP crystal under the laser irradiation with the wavelength of 1064 nm.
Comparative example 2:
compared with # 1 in example 1, the same is for the most part, except that hydrofluoric acid is used instead of nitric acid, which is the raw material added.
Detecting to obtain CsZrF4(IO3) The crystal structure data of the sample is
α ═ β ═ γ ═ 90 °, Z ═ 4, and unit cell volume
The prepared CsZrF4(IO3) The sample yield was reduced by about 40% compared to # 1 in example 1, and the crystal grain size was about 0.03-0.2mm, which was significantly reduced compared to # 1 in example 1.
The prepared CsZrF4(IO3) The crystal hasAnd large frequency doubling effect, wherein the intensity of frequency doubling signals is 4.5 times that of KDP crystals under laser irradiation with a wavelength of 1064 nm.
The embodiments described above are described to facilitate an understanding and use of the invention by those skilled in the art. It will be readily apparent to those skilled in the art that various modifications to these embodiments may be made, and the generic principles described herein may be applied to other embodiments without the use of the inventive faculty. Therefore, the present invention is not limited to the above embodiments, and those skilled in the art should make improvements and modifications within the scope of the present invention based on the disclosure of the present invention.
Claims (9)
1. The second-order non-linear optical crystal of zirconium cesium fluoroiodate is characterized by having a chemical formula of CsZrF4(IO3)；
The nonlinear optical crystal belongs to an orthorhombic system, the space group is Ima2, the unit cell parameter is
α ═ β ═ γ ═ 90 °, Z ═ 4, and unit cell volume
2. The method for preparing the cesium zirconium oxyfluoride second-order nonlinear optical crystal as claimed in claim 1, wherein a zirconium source, a cesium source, an iodine source, a fluorine source, nitric acid and water are mixed to obtain an initial mixture, and the initial mixture is crystallized under hydrothermal conditions to obtain a target product.
3. The method for preparing the cesium zirconium oxyiodide second-order nonlinear optical crystal according to claim 2, wherein the ratio of zirconium element, cesium element, iodine element, fluorine element, nitric acid and water in the initial mixture is 1mmol: (0.5-20) mmol: (0.5-50) mmol: (1-50) mmol: (0-4) mL: (0.5-10) mL.
4. The method for preparing the cesium zirconium oxyiodide second-order nonlinear optical crystal according to claim 2, wherein the zirconium source is zirconium nitrate, zirconyl nitrate, zirconium oxide or zirconium hydroxide;
the cesium source is cesium fluoride, cesium carbonate or cesium nitrate;
the iodine source is diiodo pentoxide, iodic acid or periodic acid;
the fluorine source is cesium fluoride or hydrofluoric acid.
5. The method for preparing a cesium zirconium oxyiodide second-order nonlinear optical crystal as claimed in claim 2, wherein the hydrothermal condition is at a temperature of 150-230 ℃ and the crystallization time is not less than 24 h.
6. The preparation method of the cesium zirconium oxyiodide second-order nonlinear optical crystal as claimed in claim 2, wherein after crystallization is completed, the obtained product is cooled to room temperature at a cooling rate of 0.5-15 ℃/h, and then filtered and cleaned to obtain the target product.
7. The method for preparing the second-order nonlinear optical crystal of cesium zirconium oxyiodide as claimed in claim 2, wherein the crystallization process is performed in a closed reaction vessel.
8. The use of a cesium zirconium oxyfluoride second-order nonlinear optical crystal as claimed in claim 1, for variable frequency output of visible, mid-and far-infrared laser.
9. The use of a cesium zirconium oxyiodide second-order nonlinear optical crystal according to claim 8, wherein the second-order nonlinear optical crystal is used for preparing a frequency-doubled generator, an optical parametric oscillator, an optical parametric amplifier or a photoelectric rectifier.
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| CN1382839A (en) * | 2002-03-22 | 2002-12-04 | 武汉大学 | Non-linear optical infrared crystal and its preparing process |
| CN109338471A (en) * | 2018-11-28 | 2019-02-15 | 同济大学 | A kind of mid-infrared light frequency-doubling crystal fluoro tungsten Potassiumiodate material and preparation and application |
| CN111719182A (en) * | 2020-03-12 | 2020-09-29 | 同济大学 | Europium iodate monohydrate infrared nonlinear optical crystal material and preparation and application thereof |
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| Third-order nonlinear optical materials：practical issues and theoretical challenges;Marek Samoc;《Original Paper》;20111231;2183-2189 * |
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