CN114232099A - Inorganic compound crystal, preparation method thereof and application of inorganic compound crystal as nonlinear optical crystal - Google Patents
Inorganic compound crystal, preparation method thereof and application of inorganic compound crystal as nonlinear optical crystal Download PDFInfo
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Abstract
The application discloses an inorganic compound crystal, a preparation method thereof and application of the inorganic compound crystal as a nonlinear optical crystal, wherein the chemical formula is [ K3Cl][MnGa6S12]. Has a non-centrosymmetric structure, belongs to a trigonal system and has a space group P31 c. Cell parameters of
Description
Technical Field
The invention belongs to the technical field of preparation of infrared nonlinear optical crystal materials, and relates to an inorganic compound crystal, a preparation method thereof and application of the inorganic compound crystal as a nonlinear optical crystal.
Background
The frequency conversion effect of infrared nonlinear optical (IR-NLO) materials is a convenient and efficient method for generating high power infrared laser beams. The technology has important value in laser science research, and is widely applied to the fields of industrial processing, noninvasive medical diagnosis, signal communication and the like. The applicable IR-NLO material should have several features: strong nonlinear effect, high laser damage threshold, matching, wider infrared transmission range (covering two important atmospheric windows) and good mechanical performance. Although a small proportion of IR-NLO has been commercially available, e.g. ZnGeP2(ZGP),AgGaS2(AGS),AgGaSe2(AGSe), but most suffer from some drawbacks, and there are still few IR-NLOs that can fully meet the above requirements. Therefore, the task of searching for an IR-NLO with excellent performance to replace an imperfect commercial crystal is still very difficult, and is one of the focus, hot spot and difficulty of research in the nonlinear field.
Disclosure of Invention
In order to obtain a novel infrared nonlinear optical crystal material with excellent comprehensive performance, the application provides the following scheme:
according to one aspect of the present application, there is provided a crystal of an inorganic compound, the crystal having a chemical formula of [ K3Cl][MnGa6S12]。
The inorganic compound crystal is a typical fused salt host-guest compound, and the host has [ Mn2Ga6S12]2–Three-dimensional anionic framework structure of three GaS4Of composition [ Ga3S9]Trimer with MnS6The S atoms in the octahedron are linked to form [ MnGa ]3S6]–One-dimensional chain, in which 6 chains are connected by Ga-S bond to form an inner diameter ofThe nano-tunnel of (2); object [ K ]6Cl]5+Forming [ K ] in the c-direction by face-to-face chaining3Cl]2+One-dimensional anionic chains.
The inorganic compound crystal is of a non-centrosymmetric structure, belongs to a trigonal system, and has a space group of P31 c.
The crystal cell parameters of the inorganic compound crystal are α=90.0°,β=90.0°,γ=120.0°,V=638.0~638.1,Z=1。
Further, the crystal of the inorganic compound has a unit cell parameter of α=90.0°,β=90.0°,γ=120.0°,V=638.04(5),Z=1。
The nonlinear intensity of the inorganic compound crystal is AgGaS when the incident laser is 1910nm20.7-1 times of; the optical band gap is 3.1-3.2 eV; when the incident laser is 1064nm, the laser damage threshold is AgGaS212-13 times of the total weight of the powder.
Further, the nonlinear intensity of the inorganic compound crystal is AgGaS when the incident laser light is 1910nm20.7 times of the total refractive index of the mixed laser, an optical band gap of 3.17eV, and a laser damage threshold value of AgGaS at 1064nm incident laser212.5 times of.
According to another aspect of the present application, there is provided a method for preparing the above inorganic compound crystal by a high temperature solid phase method, comprising the steps of:
mixing raw materials containing a lanthanum source, a manganese source, a gallium source, a sulfur source and potassium chloride, and crystallizing for 72-120 hours at the crystallization temperature of 850-950 ℃ to obtain the inorganic compound crystal.
The lanthanum source is selected from elementary lanthanum; the manganese source is selected from manganese simple substance; the gallium source is selected from elementary gallium; the sulfur source is selected from elemental sulfur;
optionally, the elementary lanthanum, the elementary manganese, the elementary gallium and the elementary sulfur are in powder form;
the molar ratio of lanthanum to manganese to gallium to sulfur to potassium chloride in the raw materials is 1-1.2: 0.4-0.5: 1.4-1.5: 3.3-3.4: 2.2 to 2.3;
optionally, the molar ratio of lanthanum, manganese, gallium, sulfur and potassium chloride in the feedstock is 1.16:0.48:1.43:3.35: 2.28.
the high temperature solid phase method comprises the following steps:
(1) heating for 5-7 h to 250-300 ℃, and preserving heat for 5-7 h;
(2) continuously heating for 5-7 h to 550-650 ℃, and preserving heat for 5-7 h;
(3) continuously heating for 10-15 h to reach 850-950 ℃, and preserving heat for 72-120 h;
(4) cooling to 400 ℃ at the speed of 3 ℃/h, and then cooling;
alternatively, the high temperature solid phase process comprises the steps of:
(1) heating for 6h to 300 ℃, and keeping the temperature for 6 h;
(2) continuously heating for 6h to 600 ℃, and keeping the temperature for 6 h;
(3) continuously heating for 12h to 900 ℃, and keeping the temperature for 96 h;
(4) the temperature was reduced to 400 ℃ at a rate of 3 ℃/h and subsequently cooled.
The high temperature solid phase process is carried out under vacuum. The vacuum degree of the vacuum is 1 x 10-4Pa。
Specifically, the preparation process is as follows:
mixing raw materials of lanthanum, manganese, gallium, sulfur and potassium chloride according to the molar ratio of La to Mn to Ga to S to KCl of 1.16 to 0.48 to 1.43 to 3.35 to 2.28, uniformly mixing, filling into a quartz tube, and vacuumizing to 1 x 10-4Pa sealing the tube, putting the tube into a muffle furnace, heating the tube to 300 ℃ for 6h, preserving heat for 6h, heating the tube to 600 ℃ for 6h, preserving heat for 6h, heating the tube to 900 ℃ for 12h, preserving heat for 96h, cooling the tube to 400 ℃ at the speed of 3 ℃/h, turning off the muffle furnace, and naturally cooling the tube to room temperature to obtain the chemical formula [ K3Cl][Mn2Ga6S12]The compound of (1). Here, La is used as a reaction-only promoter, and is not incorporated into the structure, and this compound cannot be synthesized without adding La.
According to another aspect of the present application, there is provided a nonlinear optical crystal characterized by comprising the above inorganic compound crystal or the inorganic compound crystal produced by the above production method.
The application has the advantages that:
the present application provides a molecular formula of [ K ]3Cl][MnGa6S12]The nonlinear optical crystal material has the nonlinear strength of AgGaS20.7 times of the total energy, the band gap reaches 3.17eV, and the laser damage threshold reaches AgGaS212.5 times of the total surface area of the crystal material, the nonlinear optical crystal material has a proper nonlinear effect and a higher laser damage threshold value, and is a novel infrared nonlinear optical (IR-NLO) crystal material with excellent comprehensive performance.
The nonlinear optical crystal material is a salt inclusion system, the structure flexibility of the salt inclusion system can adjust the crystal field of magnetic ions, good opportunity is provided for inhibiting d-d transition, and d-s and d-p transition with NLO activity is allowed to be generated. Compounds of the patent [ K3Cl][Mn2Ga6S12]Mn in (1)2+Is effectively inhibited, while Mn2+The d-orbital of (a) significantly contributes to the NLO efficiency of the compound through other transitions, giving it a strong matching SHG intensity, a high LIDT, and the widest optical bandgap (3.17eV) of all magnetic infrared NLO chalcogenides.
Drawings
FIG. 1 is a schematic structural view of the compound obtained in example 1.
FIG. 2 is a comparison of an X-ray diffraction pattern (simulated value) obtained by fitting the compound obtained in example 1 with a pattern (experimental value) obtained by X-ray diffraction measurement after grinding into powder.
FIG. 3 is a graph showing a phase matching test of the compound obtained in example 1.
FIG. 4 is a non-linear intensity plot of the compound obtained in example 1.
FIG. 5 is a UV diffuse reflectance spectrum of the compound obtained in example 1.
Detailed Description
The present application will be described in detail with reference to examples, but the present application is not limited to these examples.
Unless otherwise specified, the raw materials in the examples of the present application were all purchased from alatin reagent (shanghai) ltd, in which the purity of lanthanum source, manganese source, gallium source, and sulfur source were all 99.99%, and the purity of potassium chloride was 99%.
The analysis method in the examples of the present application is as follows:
single crystal X-ray diffraction instrument used: rigaku FR-X micro focusing diffractometer, test conditions: 293K, structural analysis using SHELXTL crystallography software.
Powder X-ray diffraction instrument used: rigaku Flex 600X-ray diffractometer, test conditions: 293K.
Measurement of nonlinear effects: testing an instrument: the light source is provided by an OPOTEK Virbrant high-energy integrated OPO laser; the output signal is collected by a Charge Coupled Detector (CCD). And (3) testing conditions are as follows: wavelength: 1910nm, output energy: 2mJ, pulse width: 10ns, frequency: 10 Hz.
Laser damage threshold test: and (3) testing conditions are as follows: wavelength: 1064 nm; the working frequency is as follows: 1 HZ; pulse width 10 ns; laser energy: 1-250mJ adjustable; using the focal length f of the lens to be 20 cm; reference sample: AGS with a particle size of 150-.
Ultraviolet diffuse reflection (optical band gap) test: testing an instrument: lambda 950 UV-Vis-NIR spectrometer; and (3) testing conditions are as follows: 293K; test range: 200 and 2500 nm.
Example 1
Nonlinear optical crystal [ K ] of formula3Cl][MnGa6S12]The preparation of (1):
uniformly mixing La simple substance (66.41mg), Mn simple substance (26.27mg), Ga simple substance (100.01mg), S simple substance (107.32mg) and KCl (170mg), filling into a quartz tube, and vacuumizing to 1 x 10-4And (3) Pa sealing the tube, putting the tube into a muffle furnace, heating the tube to 300 ℃ for 6h, preserving heat for 6h, heating the tube to 600 ℃ for 6h, preserving heat for 6h, heating the tube to 900 ℃ for 12h, preserving heat for 96h, cooling the tube to 400 ℃ at the speed of 3 ℃/h, closing the muffle furnace, and naturally cooling the tube to room temperature to obtain a product.
And (3) performing single crystal X-ray diffraction analysis on the product single crystal, adopting a Rigaku FR-X micro-focusing diffractometer under the test condition of 293K, and performing structure analysis through SHELXTL crystallography software to obtain a structure schematic diagram shown in figure 1. From FIG. 1, it can be seen that [ Mn ] is predominant2Ga6S12]2–A three-dimensional anionic framework having the structure: by three GaS4Of composition [ Ga3S9]By sharing an S atom with Mn (forming MnS)6Octahedron) to form [ MnGa ]3S6]–One-dimensional chain, in which 6 chains are connected by Ga-S bond to form an inner diameter ofThe nano-tunnel of (1). The guest is [ K ]3Cl]2+One-dimensional anionic chain, mainly composed of [ K ]6Cl]5+And forming a one-dimensional chain along the c direction through surface-to-surface linking.
Grinding the product into powder, performing powder X-ray diffraction analysis, adopting a Rigaku Flex 600X-ray diffractometer under the test condition of 293K to obtain a graph 2, and comparing a graph (experimental value) obtained by X-ray diffraction test after grinding into powder with an X-ray diffraction graph (simulated value) obtained by fitting data of single crystal X-ray diffraction analysis.
The above characterization shows that the product has a chemical formula of [ K3Cl][MnGa6S12]The compound of (1).
Test example 1
For the compound [ K ] obtained in example 13Cl][MnGa6S12]The non-linear effect of (a) is measured.
The powder crystals were sieved into five particle sizes, respectively: 30-50, 50-75, 75-100, 100-150 and 150-200 mu m, and respectively testing the nonlinear strength of the sample with each particle size and the AGS standard sample at 955nm by adopting a Kurtz-Perry method.
The adopted light source is an OPOTEK Virbrant high-energy integrated OPO laser, and output signals are collected by a Charge Coupled Detector (CCD). The test conditions were as follows: the wavelength is 1910nm, the output energy is 2mJ, the pulse width is 10ns, and the frequency is 10 Hz.
FIG. 3 shows Compound [ K ] obtained in example 13Cl][MnGa6S12]FIG. 4 is a graph showing a phase matching test of the compound [ K ] obtained in example 13Cl][MnGa6S12]Non-linear intensity map of (a).
As can be seen from the figure, the compound [ K ] obtained in example 13Cl][MnGa6S12]The nonlinear strength of the composite material is positively correlated with the particle size, and the composite material meets the phase matching requirement. When the incident laser of a sample with the particle size of 150-200 mu m is 1910nm, the nonlinear intensity is AgGaS2(AGS) 0.7 times.
Test example 2
For the compound [ K ] obtained in example 13Cl][MnGa6S12]And carrying out laser damage threshold test.
The test conditions were as follows: the wavelength is 1064 nm; the working frequency is 1 HZ; the pulse width is 10 ns; the laser energy range is 1-250 mJ; using the focal length f of the lens to be 20 cm; AGS (same as the particle size of the test sample) with the particle size of the reference sample being 150-200 mu m in the peripheral particle size.
The test protocol was as follows: the R-on-1 method is used, i.e. irradiation with successively increasing energies is performed for a point on the optical element until damage occurs at this point. And finally, according to the formula: i ═ E/(π r)2τp) Calculating to obtain laser damage threshold, wherein r is laser spot size and taupIs the pulse width.
The test results are shown in Table 1.
TABLE 1 laser Damage threshold and test parameters
Test example 3
For the compound [ K ] obtained in example 13Cl][MnGa6S12]An optical bandgap test was performed.
The test protocol was as follows: spreading the sample uniformly over the BaSO4Is placed on the surface of the Lambda 950And scanning the wave band of 200-2500nm in a sample bin of the UV-Vis-NIR spectrometer to obtain the ultraviolet diffuse reflection absorption spectrum. Applying Kubelka-Munk function α/S ═ (1-R)2The data are processed by/2R, where α is the absorption coefficient, S is the scattering coefficient, and R is the reflectance. The wavelength λ is converted to energy E using the equation 1240/λ. And drawing by taking alpha/S as an ordinate and E as an abscissa, wherein the value of the abscissa corresponding to the intersection point of the tangent of the linear segment of the ordinate and the tangent of the linear segment of the abscissa is the optical band gap of the compound.
FIG. 5 shows Compound [ K ] obtained in example 13Cl][MnGa6S12]Ultraviolet diffuse reflection absorption spectrogram.
Although the present application has been described with reference to a few embodiments, it should be understood that various changes, substitutions and alterations can be made herein without departing from the spirit and scope of the application as defined by the appended claims.
Claims (10)
1. An inorganic compound crystal characterized in that the crystal has the chemical formula [ K3Cl][MnGa6S12]。
2. The inorganic compound crystal according to claim 1, wherein the inorganic compound crystal has [ Mn [ ]2Ga6S12]2–Three-dimensional anionic framework structure of three GaS4Of composition [ Ga3S9]Trimer with MnS6The S atoms in the octahedron are linked to form [ MnGa ]3S6]–One-dimensional chain, in which 6 chains are connected by Ga-S bond to form an inner diameter ofThe nano-tunnel of (2); [ K ]6Cl]5+Forming [ K ] in the c-direction by face-to-face chaining3Cl]2+One-dimensional anionic chains.
3. The inorganic compound crystal according to claim 1, wherein the inorganic compound crystal has a non-centrosymmetric structure, belongs to a trigonal system, and has a space group of P31 c.
6. The inorganic compound crystal according to claim 1, wherein the nonlinear intensity of the inorganic compound crystal at 1910nm of incident laser light is AgGaS20.7-1 times of; the optical band gap is 3.1-3.2 eV; when the incident laser is 1064nm, the laser damage threshold is AgGaS212-13 times of the total weight of the powder.
7. A method for producing the inorganic compound crystal according to any one of claims 1 to 6, which comprises the steps of:
mixing raw materials containing a lanthanum source, a manganese source, a gallium source, a sulfur source and potassium chloride, and crystallizing for 72-120 hours at the crystallization temperature of 850-950 ℃ to obtain the inorganic compound crystal.
8. The method of claim 7, wherein the lanthanum source is selected from elemental lanthanum; the manganese source is selected from manganese simple substance; the gallium source is selected from elementary gallium; the sulfur source is selected from elemental sulfur;
preferably, the elementary lanthanum, the elementary manganese, the elementary gallium and the elementary sulfur are in powder form;
the molar ratio of lanthanum to manganese to gallium to sulfur to potassium chloride in the raw materials is 1-1.5: 0.4-0.6: 1.4-1.6: 3.3-3.6: 2.2 to 2.5;
preferably, the molar ratio of lanthanum, manganese, gallium, sulfur and potassium chloride in the raw material is 1.16:0.48:1.43:3.35: 2.28.
9. the method of claim 7, wherein the high temperature solid phase process comprises the steps of:
(1) heating for 5-7 h to 250-300 ℃, and preserving heat for 5-7 h;
(2) continuously heating for 5-7 h to 550-650 ℃, and preserving heat for 5-7 h;
(3) continuously heating for 10-15 h to reach 850-950 ℃, and preserving heat for 72-120 h;
(4) cooling to 400 ℃ at the speed of 3 ℃/h, and then cooling;
preferably, the high temperature solid phase process comprises the steps of:
(1) heating for 6h to 300 ℃, and keeping the temperature for 6 h;
(2) continuously heating for 6h to 600 ℃, and keeping the temperature for 6 h;
(3) continuously heating for 12h to 900 ℃, and keeping the temperature for 96 h;
(4) the temperature was reduced to 400 ℃ at a rate of 3 ℃/h and subsequently cooled.
10. A nonlinear optical crystal comprising the inorganic compound crystal according to any one of claims 1 to 6 or the inorganic compound crystal produced by the production method according to any one of claims 7 to 9.
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Citations (4)
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WO2016086425A1 (en) * | 2014-12-05 | 2016-06-09 | 中国科学院福建物质结构研究所 | Nonlinear optical crystal material, method for preparation thereof, and application thereof |
WO2016086426A1 (en) * | 2014-12-05 | 2016-06-09 | 中国科学院福建物质结构研究所 | Infrared nonlinear optical crystal material, method for preparation thereof, and application thereof |
CN105887204A (en) * | 2016-07-01 | 2016-08-24 | 中国科学院福建物质结构研究所 | Inorganic compound crystal Bi(SeO3)F and preparation method and application thereof |
CN107841786A (en) * | 2017-10-31 | 2018-03-27 | 中国科学院福建物质结构研究所 | A kind of inorganic compound crystal, its preparation method and application |
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WO2016086425A1 (en) * | 2014-12-05 | 2016-06-09 | 中国科学院福建物质结构研究所 | Nonlinear optical crystal material, method for preparation thereof, and application thereof |
WO2016086426A1 (en) * | 2014-12-05 | 2016-06-09 | 中国科学院福建物质结构研究所 | Infrared nonlinear optical crystal material, method for preparation thereof, and application thereof |
CN105887204A (en) * | 2016-07-01 | 2016-08-24 | 中国科学院福建物质结构研究所 | Inorganic compound crystal Bi(SeO3)F and preparation method and application thereof |
CN107841786A (en) * | 2017-10-31 | 2018-03-27 | 中国科学院福建物质结构研究所 | A kind of inorganic compound crystal, its preparation method and application |
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