CN113897679A - Zirconium fluorosulfate second-order nonlinear optical crystal material and preparation method and application thereof - Google Patents
Zirconium fluorosulfate second-order nonlinear optical crystal material and preparation method and application thereof Download PDFInfo
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Abstract
The invention relates to a zirconium fluorosulfate second-order nonlinear optical crystal material and a preparation method and application thereof, wherein the chemical formula of the crystal material is ZrF2(SO4) Belongs to the orthorhombic system, and the space group is Pca21Cell parameter of
α ═ β ═ γ ═ 90 °, Z ═ 4, unit cellHas a volume of
Compared with the prior art, the crystal ZrF2(SO4) Under 1064nm laser irradiation, the powder SHG coefficient is KH2PO45.2 times of (KDP) and can realize phase matching under 1064nm laser irradiation.
Description
Technical Field
The invention belongs to the fields of inorganic chemistry, crystallography and nonlinear optical materials, and relates to an inorganic transition metal fluorosulfate nonlinear optical crystal, in particular to a zirconium fluorosulfate second-order nonlinear optical crystal material and a preparation method and application thereof.
Background
Nonlinear optical (NLO) crystal materials with Second Harmonic (SHG) characteristics have important applications in precision manufacturing such as laser frequency conversion, micromachining, electro-optical modulation, lithography, and semiconductor inspection, because they can produce continuously tunable coherent light. An ideal NLO crystal should meet the following criteria: strong Second Harmonic (SHG) response, large band gap, easy growth of large-size single crystal, good physicochemical stability, and the like. However, these factors are mutually restrictive, especially between the SHG response and the bandgap. For example, NLO crystal KTiOPO4(KTP) exhibits a strong SHG response, and the narrow band gap of this material prevents its practical application in the ultraviolet region. Therefore, developing an effective NLO material with a good balance between frequency doubling effect and optical bandgap is an important research direction of the present generation.
In recent years, metal sulfates are a class of nonlinear optical crystal materials that are expected to find practical applications. Since the sulfate radicals are of nearly non-polar TdSymmetric isotropic tetrahedral unit, so the SHG signal of the material is weak.
Disclosure of Invention
The object of the invention is to solve the current tetrahedral primitive ([ SO ]4]2-) The problem of weak SHG signal of crystal material, provides a UV nonlinear optical crystal material-zirconium fluorosulfate second-order nonlinear optical crystal material with good performance, which realizes the balance between frequency doubling strength and optical band gap, and its preparation method and application.
In order to enhance the nonlinear optical response, the invention introduces d into a metal sulfate system0Transition metal ion Zr4+And obtaining the crystal material with wide band gap and strong nonlinear optical performance.
The purpose of the invention can be realized by the following technical scheme:
the invention provides a zirconium fluorosulfate second-order nonlinear optical crystal material, wherein the chemical formula of the crystal material is ZrF2(SO4)。
The molecular weight of the crystalline material is 225.29.
Preferably, the crystalline material belongs to the orthorhombic system, and the space group is Pca21Cell parameter of
α ═ β ═ γ ═ 90 °, Z ═ 4, and unit cell volume
Preferably, the crystalline material has a crystal structure of: each Zr4+Ions coordinated to four oxygen atoms and four fluorine atoms, respectively, [ ZrO ]4F4]Polyhedral units in which four oxygen atoms are respectively different from four [ SO ]4]Group attachment; adjacent [ ZrO ] of4F4]Polyhedral unit with concurrent [ F (1) and F (2)]Are connected to each other in such a way that [ ZrO ] is formed4F4]∞A layered structure; asymmetric [ SO4]The radical being located in [ ZrO4F4]∞Between the layers, an interlayer connector connecting four Zr atoms is formed to have a three-dimensional structure.
The second aspect of the invention provides a preparation method of the zirconium fluorosulfate second-order nonlinear optical crystal material, which comprises the following steps:
(1) mixing a zirconium source, a sulfur source, a fluorine source and water to form a mixed raw material;
(2) and crystallizing the mixed raw materials under a hydrothermal condition to obtain the zirconium fluorosulfate second-order nonlinear optical crystal material.
Preferably, the zirconium source is zirconium dioxide or zirconium fluoride, more preferably the zirconium source is zirconium fluoride; the sulfur source is sulfuric acid; the fluorine source is hydrofluoric acid or zirconium fluoride, and more preferably, the fluorine source is zirconium fluoride.
Preferably, the molar ratio of the zirconium element, the sulfur element, the fluorine element and the water in the mixed raw materials is 1: (0.5-50): (0.5-50): (1-50).
Further preferably, the molar ratio of the zirconium element, the sulfur element, the fluorine element and the water in the mixed raw materials is 1: (2-10): (1-10): (2-20).
Preferably, the temperature of the hydrothermal condition is 150-230 ℃, and the crystallization time is not less than 24 h. Further preferably, the hydrothermal condition temperature is 180-230 ℃, and the crystallization time is not less than 48 h.
Preferably, the preparation method further comprises the step of cooling to room temperature after crystallization, wherein the cooling rate is 0.5-15 ℃/h. Further preferably, the cooling rate is 0.5-6 ℃/h.
The zirconium fluorosulfate crystal material has great frequency doubling effect, and the frequency doubling effect of the powder is about KH under 1064nm laser irradiation2PO45.2 times of crystal and can realize phase matching. In addition, the band gap of the crystal material is 6.02eV, and the thermal stability temperature is 200 ℃. Therefore, the crystal material has wide application prospect in the field of nonlinear optics. For example, it can be applied to a laser frequency converter. The laser frequency converter is used for outputting visible light laser beams in double frequency harmonic waves.
The third aspect of the invention provides application of the zirconium fluorosulfate second-order nonlinear optical crystal material, and the crystal material is used for ultraviolet laser frequency conversion output.
Preferably, the crystal material is used in frequency doubling generators, optical parametric oscillators, optical parametric amplifiers and optoelectronic rectifiers.
Compared with the prior art, the beneficial effects of the invention include but are not limited to the following aspects:
(1) the invention provides a new inorganic crystal material zirconium fluorosulfate, which is characterized in that oxygen ions are replaced by more electronegative fluorine ions in a transition metal central polyhedron to easily form polarizable zirconium fluorosulfate polyhedral groups, so that the crystal material has a larger frequency doubling effect and is about KH under 1064nm laser irradiation2PO4The phase matching can be realized by 5.2 times of the frequency doubling strength of the crystal. In addition, the crystal material has wide transmission range in ultraviolet and visible light regions, the band gap is 6.02eV, the thermal stability temperature reaches 200 ℃, and the crystal material has wide application prospect in the fields of laser frequency conversion, photoelectric modulation, laser signal holographic storage and the like;
(2) the invention provides a preparation method of the zirconium fluorosulfate 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 fluorosulfate crystal material of the present invention may be used in laser frequency converter for outputting ultraviolet and visible laser beams in double frequency harmonic.
Drawings
FIG. 1 is a schematic representation of the crystal structure of zirconium fluorosulfate of the present invention;
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 transmission 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
A zirconium fluorosulfate second-order non-linear optical crystal material with the chemical formula of ZrF2(SO4) And the molecular weight is 225.29.
Preferably, the crystalline material belongs to the orthorhombic system, and the space group is Pca21Cell parameter of
α ═ β ═ γ ═ 90 °, Z ═ 4, and unit cell volume
Preferably, the crystalline material has a crystal structure of: each Zr4+Ions coordinated to four oxygen atoms and four fluorine atoms, respectively, [ ZrO ]4F4]Polyhedral units in which four oxygen atoms are respectively different from four [ SO ]4]Group attachment; adjacent [ ZrO ] of4F4]Polyhedral unit with concurrent [ F (1) and F (2)]Are connected to each other in such a way that [ ZrO ] is formed4F4]∞A layered structure; asymmetric [ SO4]The radical being located in [ ZrO4F4]∞Between the layers, an interlayer connector connecting four Zr atoms is formed to have a three-dimensional structure.
The preparation method of the zirconium fluorosulfate second-order nonlinear optical crystal material comprises the following steps of:
(1) mixing a zirconium source, a sulfur source, a fluorine source and water to form a mixed raw material;
(2) and crystallizing the mixed raw materials under a hydrothermal condition to obtain the zirconium fluorosulfate second-order nonlinear optical crystal material.
Preferably, the zirconium source is zirconium dioxide or zirconium fluoride, and more preferably, the zirconium source is zirconium fluoride; preferably the sulfur source is sulfuric acid; the fluorine source is preferably hydrofluoric acid or zirconium fluoride, and more preferably the fluorine source is zirconium fluoride. Preferably, the molar ratio of the zirconium element, the sulfur element, the fluorine element and the water in the mixed raw materials is 1: (0.5-50): (0.5-50): (1-50). Further preferably, the molar ratio of the zirconium element, the sulfur element, the fluorine element and the water in the mixed raw materials is 1: (2-10): (1-10): (2-20). The temperature of the hydrothermal condition is preferably 150-230 ℃, and the crystallization time is not less than 24 h. Further preferably, the hydrothermal condition temperature is 180-230 ℃, and the crystallization time is not less than 48 h. Preferably, the preparation method also comprises the step of cooling to room temperature after crystallization, wherein the cooling rate is 0.5-15 ℃/h. Further preferably, the cooling rate is 0.5-6 ℃/h.
The zirconium fluorosulfate crystal material has great frequency doubling effect, and the frequency doubling effect of the powder is about KH under 1064nm laser irradiation2PO45.2 times of crystal and can realize phase matching. In addition, the band gap of the crystal material is 6.02eV, and the thermal stability temperature is 200 ℃. Therefore, the crystal material has wide application prospect in the field of nonlinear optics. For example, it can be applied to a laser frequency converter. The laser frequency converter is used for outputting visible light laser beams in double frequency harmonic waves.
The zirconium fluorosulfate second-order nonlinear optical crystal material can be applied to ultraviolet laser frequency conversion output. Preferably, the crystal material is applicable to frequency doubling generators, optical parametric oscillators, optical parametric amplifiers and photoelectric rectifiers.
The following examples are given for the detailed implementation and specific operation of the present invention, but the scope of the present invention is not limited to the following examples.
Example 1 hydrothermal Synthesis of samples
Mixing a zirconium source, a sulfur source, a fluorine source and water according to a certain proportion to form 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 the speed of 3 ℃/h, filtering and cleaning the reaction system to obtain transparent blocky zirconium fluorosulfate 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 resolution
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 0.23X 0.19X 0.15mm3(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. ZrF2(SO4) Molecular weight of 225.29, belonging to orthorhombic system, and space group thereof is Pca21Cell parameter of
α ═ β ═ γ ═ 90 °, Z ═ 4, and unit cell volume
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 ZrF2(SO4) Molecular weight of 225.29, belonging to the orthorhombic system, whichSpace group Pca21Cell parameter of
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.
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 Transmission Spectroscopy test
The transmission spectrum test of sample # 1 was performed on an agilent Cary 5000 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 206nm to 2500 nm. The compound has a wide optical transmission range, an ultraviolet absorption cut-off edge of 206nm and a corresponding optical band gap of 6.02 eV.
Example 4 Infrared Spectroscopy testing
The infrared spectroscopy test of sample # 1 was performed on a Nicolet iS10 model fourier infrared spectrometer, zemer feishol technologies ltd. The results are shown in FIG. 4, and it can be seen from FIG. 4 that the compound 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 up to 200 ℃ and had good thermal stability.
Example 6 frequency doubling test experiments 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 fluorosulfate crystal has a large frequency doubling effect, and the frequency doubling signal intensity is KH of a reference sample under 1064nm wavelength laser irradiation2PO45.2 times of the crystal (as in fig. 6), phase matching can be achieved (as in fig. 7).
The embodiments described above are intended to facilitate the 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 (10)
1. The zirconium fluorosulfate second-order nonlinear optical crystal material is characterized in that the chemical formula of the crystal material is ZrF2(SO4)。
2. The zirconium fluorosulfate second order nonlinear optical crystalline material of claim 1 in the orthorhombic system with space group Pca21Cell parameter of
α ═ β ═ γ ═ 90 °, Z ═ 4, and unit cell volume
3. The zirconium fluorosulfate second order nonlinear optical crystal material of claim 1 or 2, wherein the crystal structure of the crystal material is: each Zr4+Ions coordinated to four oxygen atoms and four fluorine atoms, respectively, [ ZrO ]4F4]Polyhedral units in which four oxygen atoms are respectively different from four [ SO ]4]Group attachment; adjacent [ ZrO ] of4F4]Polyhedral unit with concurrent [ F (1) and F (2)]Are connected to each other in such a way that [ ZrO ] is formed4F4]∞A layered structure; asymmetric [ SO4]The radical being located in [ ZrO4F4]∞Between the layers, an interlayer connector connecting four Zr atoms is formed to have a three-dimensional structure.
4. The method for preparing a zirconium fluorosulfate second order nonlinear optical crystal material of any of claims 1 to 3, comprising the steps of:
(1) mixing a zirconium source, a sulfur source, a fluorine source and water to form a mixed raw material;
(2) and crystallizing the mixed raw materials under a hydrothermal condition to obtain the zirconium fluorosulfate second-order nonlinear optical crystal material.
5. The method for preparing a zirconium fluorosulfate second order nonlinear optical crystal material of claim 4, wherein the zirconium source is zirconium dioxide or zirconium fluoride; the sulfur source is sulfuric acid; the fluorine source is hydrofluoric acid or zirconium fluoride.
6. The method for preparing a zirconium fluorosulfate second-order nonlinear optical crystal material of claim 4, wherein the molar ratio of zirconium element, sulfur element, fluorine element and water in the mixed raw material is 1: (0.5-50): (0.5-50): (1-50).
7. The method for preparing a zirconium fluorosulfate second-order nonlinear optical crystal material of claim 6, wherein the molar ratio of zirconium element, sulfur element, fluorine element and water in the mixed raw material is 1: (2-10): (1-10): (2-20).
8. The method for preparing a zirconium fluorosulfate second order nonlinear optical crystal material of claim 4, characterized in that any one or more of the following conditions are included:
(i) the temperature of the hydrothermal condition is 150-230 ℃, and the crystallization time is not less than 24 h;
(ii) the preparation method also comprises the step of cooling to room temperature after crystallization, wherein the cooling rate is 0.5-15 ℃/h.
9. The use of the zirconium fluorosulfate second order nonlinear optical crystal material of any of claims 1 to 3, wherein the crystal material is used for ultraviolet laser frequency conversion output.
10. Use of a zirconium fluorosulfate second order nonlinear optical crystal material in accordance with claim 9, characterized in that the crystal material is used in frequency doubling generators, optical parametric oscillators, optical parametric amplifiers and optoelectronic rectifiers.
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| CN115058776A (en) * | 2022-06-22 | 2022-09-16 | 同济大学 | Wide band gap fluorotungstic acid fluoroiodate mid-infrared nonlinear optical crystal material and preparation and application thereof |
| CN115058776B (en) * | 2022-06-22 | 2023-11-03 | 同济大学 | Infrared nonlinear optical crystal material in wide-band-gap fluorotungstate fluoroiodate, and preparation and application thereof |
| CN115404545A (en) * | 2022-08-29 | 2022-11-29 | 同济大学 | Hafnium oxygen fluorine compound second-order nonlinear optical crystal material and preparation and application thereof |
| CN115404545B (en) * | 2022-08-29 | 2024-02-27 | 同济大学 | Hafnium oxyfluoride second-order nonlinear optical crystal material and preparation and application thereof |
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