CN113802182B - Inorganic compound crystal, preparation method and application thereof - Google Patents
Inorganic compound crystal, preparation method and application thereof Download PDFInfo
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- CN113802182B CN113802182B CN202010544236.7A CN202010544236A CN113802182B CN 113802182 B CN113802182 B CN 113802182B CN 202010544236 A CN202010544236 A CN 202010544236A CN 113802182 B CN113802182 B CN 113802182B
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Abstract
The application discloses an inorganic compound crystal, a preparation method and application thereof. The chemical formula of the inorganic compound crystal is Pb 2 GaF 2 (SeO 3 ) 2 Br belonging to monoclinic system with space group P2 1 Cell parameter of
α = γ =90.000 °, β =111.026 °, Z =4. The inorganic compound crystal is prepared by a hydrothermal method. The inorganic compound crystal Pb 2 GaF 2 (SeO 3 ) 2 The powder SHG coefficient of Br under 1064nm laser irradiation is KH 2 PO 4 The (KDP) is 5.2 times of that of the (KDP), and the phase matching can be realized under the irradiation of 1064nm laser, so that the (KDP) has good potential utilization value as a nonlinear optical material.
Description
Technical Field
The application relates to an inorganic crystal material, a preparation method and application thereof, belonging to the field of inorganic materials.
Background
The nonlinear optical crystal is a functional material widely applied to the field of photoelectric technology, and can realize laser frequency conversion, modulation of laser intensity and phase, holographic storage of laser signals and the like.
The nonlinear optical crystal in practical application at present comprises LiB 3 O 5 (LBO),β-BaB 2 O 4 (BBO),KH 2 PO 4 (KDP),KTiOPO 4 (KTP)，α-LiIO 3 And the like. With the development of laser technology and the emergence of tunable lasers, nonlinear optical devices develop rapidly, and laser frequency doubling, frequency mixing, parametric oscillation and amplification are achieved; electro-optical modulation, deflection, Q-switching, and photorefractive devices, etc. occur sequentially. The research and application of the above have provided more and more for nonlinear optical materialsThe requirement of high physical and chemical properties also promotes the rapid development of nonlinear optical materials. The second-order nonlinear optical crystal material must have a non-centrosymmetric structure.
Disclosure of Invention
According to one aspect of the present application, there is provided a crystalline Pb of an inorganic compound 2 GaF 2 (SeO 3 ) 2 Br is added. The inorganic compound crystal shows strong frequency doubling effect, and the powder SHG coefficients of the inorganic compound crystal are KH 2 PO 4 The (KDP) is 5.2 times of that of the (KDP), and the phase matching can be realized, so that the (KDP) is a nonlinear optical material with potential application value.
The inorganic compound crystal has a chemical formula of Pb 2 GaF 2 (SeO 3 ) 2 Br belonging to monoclinic system, space group is P2 1 。
Alternatively, the inorganic compound crystal Pb 2 GaF 2 (SeO 3 ) 2 Cell parameter of Br of
α＝γ＝90.000°，β＝111.026°，Z＝4。
Preferably, the unit cell parameters are
Further preferably, the unit cell parameters are
Even more preferably, the unit cell parameter is
α＝γ＝90°，β＝111.026°，Z＝4。
The inorganic compound crystal Pb 2 GaF 2 (SeO 3 ) 2 The crystal structure of Br is shown in FIG. 1. Wherein, (GaO) 3 F 3 ) 6- Octahedra are connected through a common vertex to form a one-dimensional chain, se (1) O 3 2- And Se (2) O 3 2- The groups are connected to octahedral chains by means of bridging and suspending, respectively, to form [ GaF 2 (SeO 3 ) 2 ] 3- One-dimensional anionic chains (FIG. 1 a). It is noteworthy that there are three ligand sites in the octahedron, namely a terminal site (attached to only one metal atom), a bridging site (attached to two Ga atoms) and a shared site (attached to one Ga atom and one Se atom). Pb 2+ And Br - Ions form a one-dimensional [ Pb ] along the b-axis 2 Br] 3+ Cationic chain at [ GaF ] 2 (SeO 3 ) 2 ] 3- Interchain (FIG. 1b, FIG. 1 c).
Optionally, the ultraviolet absorption cutoff wavelength of the inorganic compound crystal is 250 to 290nm.
Alternatively, the ultraviolet absorption cutoff wavelength of the inorganic compound crystal is 270nm.
Optionally, the inorganic compound crystals have a weight loss of no more than 5% at 465 ℃.
Optionally, the inorganic compound crystals have a weight loss of no more than 3% at 465 ℃.
Optionally, the inorganic compound crystal has a weight loss of not more than 5% at 465 ℃, and the phase does not change.
I.e. inorganic compound crystal Pb 2 GaF 2 (SeO 3 ) 2 Br, can be stabilized to 465 ℃.
According to still another aspect of the present application, there is provided the above-mentioned inorganic compound crystalline Pb 2 GaF 2 (SeO 3 ) 2 A preparation method of Br, which comprises the following steps,the preparation method has simple process, and can obtain inorganic compound crystal Pb with high purity and high crystallinity 2 GaF 2 (SeO 3 ) 2 A Br material.
The preparation method of the inorganic compound crystal adopts a hydrothermal crystallization method to crystallize a raw material mixture containing lead element, gallium element, fluorine element, selenium element, bromine element and water at the temperature of 180-250 ℃.
Optionally, in the raw material mixture, the molar ratio of the lead element, the gallium element, the fluorine element, the selenium element, the bromine element, and the water is:
Pb：Ga：F：Se：Br：H 2 O＝0.4～1.3：0.4～2.5：0.5～5.0：1～5：0.5～2.6：150～500。
optionally, in the raw material mixture, the molar ratio of the lead element, the gallium element, the fluorine element, the selenium element, the bromine element, and the water is:
Pb：Ga：F：Se：Br：H 2 O＝0.8～1.3：0.8～2.5：2～5.0：2～5：1～2.6：200～500。
optionally, in the raw material mixture, the molar ratio of the lead element, the gallium element, the fluorine element, the selenium element, the bromine element, and the water is:
Pb：Ga：F：Se：Br：H 2 O＝0.5～1：0.8～2：0.4～5：2～4：1～2：200～500。
optionally, in the raw material mixture, the molar ratio of the lead element, the gallium element, the fluorine element, the selenium element, the bromine element, and the water is:
Pb：Ga：F：Se：Br：H 2 O＝0.8～1.1：0.8～2：2～3：2～4：1～2：200～400。
optionally, in the raw material mixture, the lead element is at least one of lead carbonate, lead nitrate, lead chloride, lead oxide, lead fluoride, lead bromide and lead metaborate; the gallium element is at least one of gallium oxide, gallium nitrate, gallium chloride and gallium sulfate; the fluorine element is at least one of hydrofluoric acid, lead fluoride and fluoroboric acid; selenium element is at least one of selenium dioxide, selenic acid, zinc selenite, lead selenite and sodium selenite; bromine is at least one of lead bromide, hydrobromic acid, gallium tribromide and sodium bromide.
Optionally, in the raw material mixture, the lead element is derived from lead bromide; the gallium element comes from gallium oxide; the fluorine element is derived from hydrofluoric acid; the selenium element is from selenium dioxide; bromine is derived from lead bromide.
Optionally, the hydrofluoric acid is an aqueous solution of hydrofluoric acid, and the concentration of the aqueous solution is 40wt% to 100wt%.
Optionally, the crystallization temperature is 180-230 ℃, and the crystallization time is not less than 6 hours.
Optionally, the crystallization temperature is 200 ℃ to 230 ℃, and the crystallization time is 30 hours to 120 hours.
Optionally, the upper limit of the crystallization temperature is selected from 250 ℃, 240 ℃, 230 ℃, 220 ℃, 210 ℃, 200 ℃, or 190 ℃; the lower limit is selected from 180 deg.C, 190 deg.C, 200 deg.C, 210 deg.C, 220 deg.C, 230 deg.C or 240 deg.C.
Optionally, the upper limit of the crystallization time is selected from 120h, 110h, 100h, 96h, 80h, 72h, 70h, 60h, 50h, 48h, or 40h; the lower limit is selected from 30h, 40h, 48h, 50h, 60h, 70h, 80h, 96h, 100h or 110h.
Alternatively, the method for producing the inorganic compound crystal comprises the steps of:
(a) Crystallizing a raw material mixture containing lead element, gallium element, fluorine element, selenium element, bromine element and water at a crystallization temperature of 180-250 ℃ for more than 24 hours;
(b) And after crystallization is finished, cooling the system to room temperature at a cooling rate of no more than 15 ℃/h, and separating and drying to obtain a solid sample, namely the inorganic compound crystal.
As a preferred embodiment, the method for producing the crystals of the inorganic compound comprises the steps of:
(a) Placing a raw material mixture containing lead element, gallium element, fluorine element, selenium element, bromine element and water in a high-pressure reaction kettle with a polytetrafluoroethylene lining, sealing, and crystallizing at a crystallization temperature of 180-250 ℃ for more than 24 hours;
(b) And after crystallization is finished, cooling the system to room temperature at a cooling rate of no more than 15 ℃/h, and separating and drying to obtain a solid sample, namely the inorganic compound crystal.
Optionally, the cooling rate in the step (b) is 0.5-13 ℃/h.
Further optionally, the cooling rate in the step (b) is 0.5-6 ℃/h.
Optionally, the upper limit of the cooling rate is selected from 13 ℃/h, 10 ℃/h, 8 ℃/h, 6 ℃/h, 4 ℃/h, 3 ℃/h, 2 ℃/h or 1 ℃/h; the lower limit is selected from 0.5 deg.C/h, 1 deg.C/h, 2 deg.C/h, 3 deg.C/h, 4 deg.C/h, 6 deg.C/h, 8 deg.C/h or 10 deg.C/h.
The shape of the inorganic compound crystal prepared by the hydrothermal method is a colorless and transparent massive crystal.
According to still another aspect of the present application, there is provided the crystalline Pb of the inorganic compound 2 GaF 2 (SeO 3 ) 2 Br, inorganic compound crystal Pb prepared by the preparation method of the inorganic compound crystal 2 GaF 2 (SeO 3 ) 2 The application of Br as nonlinear optical crystal material.
The nonlinear optical crystal material contains the inorganic compound crystal Pb 2 GaF 2 (SeO 3 ) 2 Br, crystalline Pb of inorganic Compound obtained by any of the above-mentioned methods 2 GaF 2 (SeO 3 ) 2 Br。
Inorganic compound crystal Pb 2 GaF 2 (SeO 3 ) 2 Br outputs strong 532nm green light under 1064nm laser irradiation, and the powder SHG coefficient is KH 2 PO 4 5.2 times of (KDP) and can realize phase matching.
According to still another aspect of the present application, there is provided a laser frequency converter characterized by containing the above inorganic compound crystal Pb 2 GaF 2 (SeO 3 ) 2 Br, crystalline Pb of inorganic Compound obtained by any of the above-mentioned methods 2 GaF 2 (SeO 3 ) 2 Br。
In this application, "room temperature" means 25 ℃.
In this application, all numerical ranges are inclusive of the endpoints unless specifically stated otherwise.
Benefits of the present application include, but are not limited to:
(1) The present application provides a novel inorganic compound crystal Pb 2 GaF 2 (SeO 3 ) 2 Br of KH under 1064nm laser irradiation 2 PO 4 5.2 times of (KDP) and can realize phase matching. Thus Pb 2 GaF 2 (SeO 3 ) 2 The Br crystal has good potential utilization value as a nonlinear optical material.
(2) The inorganic Compound Crystal Pb provided in the present application 2 GaF 2 (SeO 3 ) 2 Br, which has high transmittance in the spectral range of 250-2500 nm and ultraviolet absorption cut-off wavelength of about 270nm.
(3) The inorganic compound crystal Pb provided by the present application 2 GaF 2 (SeO 3 ) 2 Br, which can be stabilized to 465 ℃, and has excellent thermal stability.
(4) The present application also provides the inorganic compound crystal Pb 2 GaF 2 (SeO 3 ) 2 The preparation method of Br adopts a hydrothermal crystallization method to grow colorless blocky Pb 2 GaF 2 (SeO 3 ) 2 Crystalline Br. The method has simple process, and can obtain the inorganic compound Pb with high purity and high crystallinity 2 GaF 2 (SeO 3 ) 2 A crystalline Br material.
Drawings
FIG. 1 shows the inorganic compound Pb 2 GaF 2 (SeO 3 ) 2 A crystal structure of Br, wherein FIG. 1 (a) is [ GaF ] 2 (SeO 3 ) 2 ] 3- A one-dimensional anionic chain; FIG. 1 (b) is 1D [ Pb ] 2 Br] 3+ And 1D 2 [ GaF ] 2 (SeO 3 ) 2 ] 3- The crystal structure of (a); FIG. 1 (c) is [ Pb ] 2 Br] 3+ The cationic chains.
FIG. 2 is a comparison of the X-ray diffraction pattern obtained by fitting the crystal structure analyzed by single crystal X-ray diffraction of sample No. 1 with the pattern obtained by X-ray diffraction test after the sample is ground into powder.
Fig. 3 is an ultraviolet-visible-near infrared diffuse reflection spectrum of sample # 1.
FIG. 4 is a thermogram of sample # 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, all materials and reagents used in the present application were purchased commercially and used as received without treatment, and the equipment used was the manufacturer's recommended protocol and parameters.
Example 1 hydrothermal Synthesis of samples
Preparing raw materials according to a certain molar ratio, placing the raw materials in a high-pressure reaction kettle with a polytetrafluoroethylene lining, heating to a crystallization temperature, keeping the temperature for a period of time, and then cooling the system to room temperature at a certain cooling rate. And after suction filtration and washing, obtaining a colorless blocky crystal sample, namely the sample of the inorganic compound crystal.
The sample number, the kind and amount of raw materials, the crystallization temperature, the retention time, and the cooling rate are shown in Table 1. Wherein the HF is from an aqueous HF solution having a concentration of 40 wt%.
TABLE 1
Example 2 crystal structure resolution
Sample 1 was examined by single crystal X-ray diffraction and powder X-ray diffraction # ～5 # And (5) carrying out structure analysis.
Wherein the single crystal X-ray diffraction is carried out on a SuperNova CCD type X-ray single crystal diffractometer from Agilent, USA. The data collection temperature is 293K, and the diffraction light source is Mo-Ka ray monochromized by graphite
The scanning mode is omega-2 theta; the data were subjected to absorption correction processing using the Multi-Scan method. The structure analysis adopts a SHELXTL-2014 program packageCompleting the process; 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 F 2 The full matrix least square method refines the coordinates and anisotropic thermal parameters of all atoms.
Powder X-ray diffraction was carried out on a Miniflex type II X-ray powder diffractometer, manufactured by RIGAKU, japan, under the conditions of a fixed target monochromatic light source Cu-Ka, wavelength
The voltage and current is 30kV/15A, the scanning range is 10-70 degrees, and the scanning step length is 0.02 degree.
Wherein the single crystal X-ray diffraction results showed that sample 1 # ～5 # All chemical formulas are Pb 2 GaF 2 (SeO 3 ) 2 Br belonging to monoclinic system with space group P2 1 Cell parameter of
α = γ =90.000 °, β =111.026 °, Z =4. The inorganic compound crystal Pb 2 GaF 2 (SeO 3 ) 2 The crystal structure of Br is shown in FIG. 1. Wherein (GaO) 3 F 3 ) 6- Octahedrons are connected through a common vertex to form a one-dimensional chain, se (1) O 3 2- And Se (2) O 3 2- The groups are respectively connected on an octahedral chain in a bridging and suspending way to form [ GaF 2 (SeO 3 ) 2 ] 3- One-dimensional anionic chains (FIG. 1 a). It is noteworthy that there are three ligand sites in the octahedron, namely a terminal site (linked to only one metal atom), a bridging site (linked to two Ga atoms), and a shared site (linked to one Ga atom and one Se atom). Pb 2+ And Br - Ions form a one-dimensional [ Pb ] along the b-axis 2 Br] 3+ Cationic chain of [ GaF ] 2 (SeO 3 ) 2 ] 3- Interchain (FIG. 1b, FIG. 1 c).
As followsProduct No. 1 is typical, belongs to monoclinic system, and has space group P2 1 Cell parameter of
The powder X-ray diffraction result showed that sample 1 # ～5 # In the XRD spectrum, the peak positions are basically the same, and the intensities of various peaks are slightly different.
With sample 1 # As a typical representative, as shown in fig. 2, the obtained X-ray diffraction pattern is fitted to sample 1 based on the crystal structure resolved by single crystal X-ray diffraction # Grinding into powder, and testing by X-ray diffraction to obtain a spectrum with consistent peak position and peak intensity. Indicating that the obtained samples have high purity.
Example 3 frequency doubling test experiments and results
With sample 1 # As a representative, for the inorganic compound crystal Pb 2 GaF 2 (SeO 3 ) 2 Br was subjected to frequency doubling test.
The method comprises the following specific steps: nd with Q-switched with frequency converter: YAG solid laser generates 1064nm laser and 2.05 μm laser as fundamental frequency light to irradiate the tested crystal powder, using photomultiplier to detect the generated second harmonic, and using oscilloscope to display the harmonic intensity. Screening out crystals with different particle sizes from the crystal sample to be detected by using a standard sieve, wherein the particle sizes are 45-53 mu m, 53-75 mu m, 75-105 mu m, 105-150 mu m, 150-210 mu m and 210-300 mu m respectively. And observing the variation trend of the frequency multiplication signal along with the granularity, and judging whether the frequency multiplication signal can realize phase matching. Under the same test condition, comparing the intensity of the second harmonic generated by the sample to be tested with the reference crystal KH 2 PO 4 (KDP) the intensity of the second harmonic generated, thereby obtaining the relative magnitude of the sample doubling effect.
The test result shows that the compound Pb 2 GaF 2 (SeO 3 ) 2 The powder SHG coefficient of Br under 1064nm laser irradiation is KH 2 PO 4 (KDP) of 5.2 times, and can realize phase matching.
Example 4 diffuse reflectance absorption Spectroscopy testing
With sample 1 # As a representative, for the inorganic compound crystal Pb 2 GaF 2 (SeO 3 ) 2 Br was subjected to diffuse reflectance absorption spectroscopy on a UV-VIS-NIR spectrophotometer model Lambda-950 from Perkin-Elmer, USA. Grinding the crystal sample into powder with BaSO 4 As a reference substrate. The results of the test are shown in FIG. 3, which indicates that the compound Pb is 2 GaF 2 (SeO 3 ) 2 The Br crystal has wide transmission range, high transmittance in the spectral range of 250-2500 nm, and ultraviolet absorption cut-off wavelength of about 270nm.
Example 5 thermogravimetric analysis of samples
With sample 1 # As a representative, for the inorganic compound crystal Pb 2 GaF 2 (SeO 3 ) 2 Thermogravimetric analysis was performed on Br on a thermogravimetric analyzer STA 449F3 from NETZSCH, germany, and the results are shown in fig. 4. As can be seen from the figure, pb 2 GaF 2 (SeO 3 ) 2 The Br crystals can be stabilized to 465 ℃.
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 (18)
1. An inorganic compound crystal characterized in that the chemical formula of the inorganic compound crystal is Pb 2 GaF 2 (SeO 3 ) 2 Br belonging to monoclinic system with space group P2 1 ；
The inorganic compound crystal Pb 2 GaF 2 (SeO 3 ) 2 Cell parameter of Br of
α＝γ＝90.000°，β＝111.026°，Z＝4。
2. The inorganic compound crystal according to claim 1, wherein the unit cell parameter is
3. The inorganic compound crystal according to claim 1, wherein the ultraviolet absorption cutoff wavelength of the inorganic compound crystal is 250 to 290nm.
4. The inorganic compound crystal according to claim 1, wherein the ultraviolet absorption cutoff wavelength of the inorganic compound crystal is 270nm.
5. The inorganic compound crystal according to claim 1, wherein the inorganic compound crystal has a weight loss of not more than 5% at 465 ℃.
6. The method for producing the inorganic compound crystal according to any one of claims 1 to 5, wherein the inorganic compound crystal is produced by a hydrothermal method by crystallizing a raw material mixture containing lead, gallium, fluorine, selenium, bromine and water at a temperature of 180 to 250 ℃.
7. The method for producing an inorganic compound crystal according to claim 6,
in the raw material mixture, the molar ratio of lead element, gallium element, fluorine element, selenium element, bromine element and water is as follows:
Pb：Ga：F：Se：Br：H 2 O＝0.4～1.3：0.4～2.5：0.5～5.0：1～5：0.5～2.6：
150～500。
8. the method for producing an inorganic compound crystal according to claim 6, wherein the raw material mixture contains lead, gallium, fluorine, selenium, bromine, and water in the following molar ratios:
Pb：Ga：F：Se：Br：H 2 O＝0.5～1：0.8～2：0.4～5：2～4：1～2：200～500。
9. the method of producing an inorganic compound crystal according to claim 6, wherein the raw material mixture contains lead, gallium, fluorine, selenium, bromine, and water in the following molar ratios:
Pb：Ga：F：Se：Br：H 2 O＝0.8～1.1：0.8～2：2～3：2～4：1～2：200～400。
10. the method for producing an inorganic compound crystal according to claim 6, wherein in the raw material mixture, the lead element is at least one selected from the group consisting of lead carbonate, lead nitrate, lead chloride, lead oxide, lead fluoride, lead bromide, and lead metaborate; the gallium element is at least one of gallium oxide, gallium nitrate, gallium chloride and gallium sulfate; the fluorine element is at least one of hydrofluoric acid, lead fluoride and fluoroboric acid; selenium element is at least one of selenium dioxide, selenic acid, zinc selenite, lead selenite and sodium selenite; bromine is at least one of lead bromide, hydrobromic acid, gallium tribromide and sodium bromide.
11. The method for producing an inorganic compound crystal according to claim 6, wherein in the raw material mixture, the lead element is derived from lead bromide; the gallium element comes from gallium oxide; the fluorine element is derived from hydrofluoric acid; the selenium element is from selenium dioxide; bromine is derived from lead bromide.
12. The method for producing an inorganic compound crystal according to claim 6, wherein the crystallization temperature is 180 ℃ to 230 ℃ and the crystallization time is not less than 6 hours.
13. The method for producing an inorganic compound crystal according to claim 6, wherein the crystallization temperature is 200 to 230 ℃ and the crystallization time is 30 to 120 hours.
14. The method for producing an inorganic compound crystal according to claim 6,
(a) Crystallizing a raw material mixture containing lead element, gallium element, fluorine element, selenium element, bromine element and water at a crystallization temperature of 180-250 ℃ for more than 24 hours;
(b) And after crystallization is finished, cooling the system to room temperature at a cooling rate of not more than 15 ℃/h, and separating and drying to obtain a solid sample, namely the inorganic compound crystal.
15. The method of producing an inorganic compound crystal according to claim 6, wherein the temperature decrease rate in the step (b) is 0.5 to 13 ℃/h.
16. The method for producing an inorganic compound crystal according to claim 6, wherein the temperature decrease rate in the step (b) is 0.5 to 6 ℃/h.
17. The crystalline Pb of the inorganic compound as claimed in any one of claims 1 to 5 2 GaF 2 (SeO 3 ) 2 Br, crystalline Pb of an inorganic compound produced by the method for producing crystalline Pb of an inorganic compound according to any one of claims 6 to 16 2 GaF 2 (SeO 3 ) 2 Application of Br as non-linear optical crystal material.
18. A laser frequency converter comprising the inorganic compound crystal Pb of any one of claims 1 to 5 2 GaF 2 (SeO 3 ) 2 Br according to the rightThe inorganic compound crystal Pb produced by the method for producing inorganic compound crystal according to any one of claims 6 to 16 2 GaF 2 (SeO 3 ) 2 Br。
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