CN109811409B - Mid-infrared nonlinear optical crystal material with high laser damage threshold and preparation method and application thereof - Google Patents
Mid-infrared nonlinear optical crystal material with high laser damage threshold and preparation method and application thereof Download PDFInfo
- Publication number
- CN109811409B CN109811409B CN201910166180.3A CN201910166180A CN109811409B CN 109811409 B CN109811409 B CN 109811409B CN 201910166180 A CN201910166180 A CN 201910166180A CN 109811409 B CN109811409 B CN 109811409B
- Authority
- CN
- China
- Prior art keywords
- nonlinear optical
- crystal material
- damage threshold
- mid
- laser damage
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
- 230000003287 optical effect Effects 0.000 title claims abstract description 81
- 239000000463 material Substances 0.000 title claims abstract description 72
- 239000013078 crystal Substances 0.000 title claims abstract description 58
- 238000002360 preparation method Methods 0.000 title abstract description 13
- 239000000843 powder Substances 0.000 claims abstract description 33
- 238000000034 method Methods 0.000 claims abstract description 23
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 16
- 230000005540 biological transmission Effects 0.000 claims abstract description 14
- 230000000694 effects Effects 0.000 claims abstract description 13
- 235000019796 monopotassium phosphate Nutrition 0.000 claims abstract description 13
- 238000001556 precipitation Methods 0.000 claims abstract description 11
- 230000004580 weight loss Effects 0.000 claims abstract description 8
- 229910000402 monopotassium phosphate Inorganic materials 0.000 claims abstract description 6
- PJNZPQUBCPKICU-UHFFFAOYSA-N phosphoric acid;potassium Chemical compound [K].OP(O)(O)=O PJNZPQUBCPKICU-UHFFFAOYSA-N 0.000 claims abstract description 6
- 239000000126 substance Substances 0.000 claims abstract description 6
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 26
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 18
- 239000011780 sodium chloride Substances 0.000 claims description 13
- 238000006243 chemical reaction Methods 0.000 claims description 12
- 239000012153 distilled water Substances 0.000 claims description 11
- 239000002244 precipitate Substances 0.000 claims description 7
- 239000000047 product Substances 0.000 claims description 7
- 238000001035 drying Methods 0.000 claims description 6
- 238000010438 heat treatment Methods 0.000 claims description 6
- 238000005406 washing Methods 0.000 claims description 6
- 238000001816 cooling Methods 0.000 claims description 5
- -1 polytetrafluoroethylene Polymers 0.000 claims description 4
- 238000001914 filtration Methods 0.000 claims description 3
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 3
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 3
- 238000007789 sealing Methods 0.000 claims description 3
- 238000003756 stirring Methods 0.000 claims description 3
- 238000000967 suction filtration Methods 0.000 claims description 3
- 239000002994 raw material Substances 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims 2
- 238000004519 manufacturing process Methods 0.000 abstract description 2
- 238000001308 synthesis method Methods 0.000 abstract description 2
- 238000012360 testing method Methods 0.000 description 8
- 238000010521 absorption reaction Methods 0.000 description 6
- 238000000862 absorption spectrum Methods 0.000 description 4
- 239000012612 commercial material Substances 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 4
- 229910052731 fluorine Inorganic materials 0.000 description 4
- 239000002245 particle Substances 0.000 description 4
- 238000004891 communication Methods 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- 239000011521 glass Substances 0.000 description 3
- 150000004820 halides Chemical class 0.000 description 3
- 229910052745 lead Inorganic materials 0.000 description 3
- 239000013307 optical fiber Substances 0.000 description 3
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 2
- 125000000129 anionic group Chemical group 0.000 description 2
- 230000007123 defense Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 239000011737 fluorine Substances 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- 229910007475 ZnGeP2 Inorganic materials 0.000 description 1
- 230000003321 amplification Effects 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 230000002238 attenuated effect Effects 0.000 description 1
- 229910052798 chalcogen Inorganic materials 0.000 description 1
- 150000001787 chalcogens Chemical class 0.000 description 1
- 229910052951 chalcopyrite Inorganic materials 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 230000001747 exhibiting effect Effects 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- 238000002329 infrared spectrum Methods 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 230000001678 irradiating effect Effects 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000012544 monitoring process Methods 0.000 description 1
- 238000003199 nucleic acid amplification method Methods 0.000 description 1
- 230000010355 oscillation Effects 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 238000002076 thermal analysis method Methods 0.000 description 1
Images
Landscapes
- Optical Modulation, Optical Deflection, Nonlinear Optics, Optical Demodulation, Optical Logic Elements (AREA)
Abstract
The invention discloses a mid-infrared nonlinear optical crystal material with a high laser damage threshold, a preparation method and application thereof, wherein the chemical formula of the material is Pb7F12Cl2The powder has frequency doubling effect 2 times that of potassium dihydrogen phosphate, and the powder is transparentThe over range is 0.27-20 μm; the optical band gap value is 4.5eV, and the laser damage threshold of the powder is 80MW/cm2The thermal weight loss temperature is 570 ℃; during production, the Pb is7F12Cl2The preparation is carried out by a hydrothermal reaction method or a solution precipitation method; the intermediate infrared nonlinear optical crystal material provided by the invention has a stronger second-order nonlinear optical effect capable of phase matching, has wider light transmission windows in a visible light region and an intermediate infrared light region, has a very high laser damage threshold and thermal stability, is simple to operate in a synthesis method, has high product purity, and can be widely applied to the field of optics.
Description
Technical Field
The invention relates to the technical field of inorganic chemical materials, in particular to a mid-infrared nonlinear optical crystal material with a high laser damage threshold value, and a preparation method and application thereof.
Background
Nonlinear optical effects originate from the interaction of the laser light with the medium. When laser light propagates in a medium with a non-zero second-order polarizability, nonlinear optical effects such as frequency doubling, sum frequency, difference frequency, optical parametric amplification and the like can be generated. The second-order nonlinear optical effect of the crystal can be used for manufacturing nonlinear optical devices such as a second harmonic generator, a frequency converter, an optical parametric oscillator and the like, and has important application value in many fields such as laser technology, atmospheric monitoring, national defense and military and the like. Inorganic nonlinear optical materials are dominant in practical research of second-order nonlinear optical materials. According to the light-transmitting band and the application range, the inorganic nonlinear optical crystal material can be divided into a nonlinear optical material in an ultraviolet light region, a nonlinear optical material in a visible light region and a nonlinear optical material in an infrared light region.
The intermediate infrared band nonlinear optical crystal material has very important application in the aspects of laser spectrum, optical communication, high-intensity laser weapons and the like, and is an important high and new technology material. When the laser interacts with the medium with non-central symmetrical structure, it can generate non-linear optical effect, such as frequency doubling, optical parametric oscillation and photorefractive, etc. The nonlinear optical effect of the crystal is utilized to realize the conversion of laser frequency and obtain more lasers with different wavelengths, so that a new laser source with continuously adjustable wavelength is developed, and the manufactured device can be widely applied to the fields of optical information storage, laser communication, laser countermeasure and the like.
The current commercial mid-infrared band nonlinear optical crystal material is mainly based on chalcopyrite compound of chalcogen class, such as AgGaS2、AgGaSe2、ZnGeP2Etc. which have the advantages of large nonlinear optical coefficient and good infrared transmission rangeAnd (5) enclosing. However, due to the semiconductor characteristics, the band gap of the materials is narrow, so that the laser damage threshold of the materials is low, and the application range of the materials is severely limited. Therefore, the research on the novel mid-infrared band nonlinear optical crystal material with high laser damage threshold is one of the leading edge and the major challenges in the field of the current nonlinear optical materials.
Disclosure of Invention
The invention aims to provide a mid-infrared nonlinear optical crystal material Pb with high laser damage threshold, simple preparation method and good stability7F12Cl2And a preparation method and application thereof.
The invention is realized by the following technical scheme:
the invention relates to a mid-infrared nonlinear optical crystal material with high laser damage threshold, and the chemical formula of the mid-infrared nonlinear optical crystal material is Pb7F12Cl2。
Preferably, the mid-infrared nonlinear optical crystal material Pb in the invention7F12Cl2The powder of (A) has a frequency doubling effect 2 times that of potassium dihydrogen phosphate, and has a transmission range of 0.27-20 μm.
Preferably, the mid-infrared nonlinear optical crystal material Pb in the invention7F12Cl2Has an optical band gap value of 4.5eV and a laser damage threshold of 80MW/cm2About the commercial material AgGaS2（5.2MW/cm2) 16 times of that of the product, and the thermal weight loss temperature is 570 ℃.
The invention also provides a preparation method of the mid-infrared nonlinear optical crystal material with high laser damage threshold, and the Pb is7F12Cl2The preparation method adopts a hydrothermal reaction method or a solution precipitation method.
The hydrothermal reaction method in the invention is to mix PbF2And NaCl is dissolved in the water solution to carry out hydrothermal reaction.
Preferably, the hydrothermal reaction method in the invention is to mix the raw materials in a molar ratio of 7: 2 PbF2Adding NaCl and water into a hydrothermal reaction kettle, sealing the reaction kettle, putting the reaction kettle into a muffle furnace, heating to 230 ℃ within 3h, and then adding NaClAnd (3) carrying out constant temperature reaction for 7 days, cooling to 30 ℃ at the speed of 1 ℃/h, washing the product with distilled water after cooling, carrying out suction filtration, and drying to obtain colorless transparent small crystals, namely the intermediate infrared nonlinear optical crystal material.
Furthermore, the inner lining of the reaction kettle is made of polytetrafluoroethylene.
The solution precipitation method in the invention is to precipitate PbF2And NaCl is added into the distilled water, heated and stirred to obtain white precipitate, and then the white precipitate is filtered, washed and dried.
Further, the solution precipitation method in the invention is to mix the solution with the solvent in a molar ratio of 7: 2 PbF2Adding NaCl and distilled water at 70-80 deg.C, heating and stirring to 90-100 deg.C to obtain white precipitate, filtering, washing with distilled water for 2-3 times, and drying.
The invention also provides application of the mid-infrared nonlinear optical crystal material with high laser damage threshold in the field of optics.
Since the fluorine-containing halide tends to have a larger band gap, it is advantageous to increase the laser damage threshold of the material. Therefore, a new exploration way is to find a novel mid-infrared nonlinear optical crystal material with a high laser damage threshold from fluorine-containing halides. The invention uses PbF2And NaCl as initial reactant, and preparing the intermediate infrared nonlinear optical crystal material Pb by a hydrothermal reaction method or a solution precipitation method7F12Cl2. When Pb and F are bonded with a strong metallic heavy metal atom, the Pb and F have larger band gap values, so that a higher laser damage threshold value is caused, and therefore, the intermediate infrared nonlinear optical crystal material with a high laser damage threshold value is searched from Pb-containing and F-containing halides and is a better approach. Experiments show that the frequency doubling effect of the intermediate infrared nonlinear optical crystal material powder is 2 times of KDP; phase matching can be realized; the total transmission range is 0.27-20 μm; the laser damage threshold of the powder is 80MW/cm2(ii) a The thermal weight loss temperature was 570 ℃.
The invention discloses an inorganic mid-infrared nonlinear optical material Pb7F12Cl2With [ Pb ]3F9Cl]4-As anionic groups, have incompletely counteracted distortions, can produce dipole moments, and the groups are uniformly aligned in the crystal, thereby exhibiting macroscopically nonlinear optical effects. The compound does not contain crystal water, and the light transmission range in the middle infrared region can reach 20 mu m; the ultraviolet absorption cutoff edge was 0.27. mu.m. Has very high laser damage threshold (80 MW/cm)2) About the commercial material AgGaS under the same test conditions2（5.2MW/cm2) 16 times that of KDP, and the nonlinear optical effect is 2 times that of KDP. Therefore, the material has excellent comprehensive performance and can be used as a mid-infrared nonlinear optical crystal material.
Compared with the prior art, the inorganic intermediate infrared nonlinear optical crystal material has the following advantages:
1. the powder frequency doubling effect is 2 times of that of potassium dihydrogen phosphate (KDP) as shown in a powder frequency doubling test result;
2. the laser damage threshold of the compound powder was 80MW/cm2Is the current commercial intermediate infrared nonlinear optical crystal material AgGaS2(5.2 MW/cm under equivalent test conditions)2) 16 times the laser damage threshold.
3. The powder of the compound has a wider transmission range in a visible light region and a middle infrared light region, and the transmission waveband of the powder is 0.27-20 mu m;
4. the crystal water is not contained, the air stability is realized, the thermal stability is better, and the thermal weight loss temperature reaches 570 ℃;
5. the material can be prepared by a simple hydrothermal reaction method or a solution precipitation method.
6. The intermediate infrared nonlinear optical crystal material provided by the invention has a stronger second-order nonlinear optical effect capable of phase matching, has wider light transmission windows in a visible light region and an intermediate infrared light region, has a very high laser damage threshold and thermal stability, is simple to operate in a synthesis method, has high product purity, and can be widely applied to the field of optics.
Drawings
FIG. 1 shows Pb in the present invention7F12Cl2Of (Pb)3F9Cl]4- A group configuration diagram;
FIG. 2 shows Pb in the present invention7F12Cl2Middle [ Pb ]3F9Cl]4-A pattern of radical arrangements;
FIG. 3 shows Pb in the present invention7F12Cl2Ultraviolet-visible-near infrared absorption spectrum of the powder;
FIG. 4 shows Pb in the present invention7F12Cl2A Fourier transform attenuated infrared absorption spectrum of the powder;
FIG. 5 shows Pb in the present invention7F12Cl2A thermal property profile of the powder;
FIG. 6 shows Pb in the present invention7F12Cl2The frequency doubling effect of the powder is phase-matched with the spectrum.
Detailed Description
Example 1
The chemical formula of the mid-infrared nonlinear optical crystal material with the high laser damage threshold is Pb7F12Cl2。
The mid-infrared nonlinear optical crystal material Pb in the embodiment7F12Cl2The powder of (A) has a frequency doubling effect 2 times that of potassium dihydrogen phosphate, and has a transmission range of 0.27-20 μm.
The mid-infrared nonlinear optical crystal material Pb in the embodiment7F12Cl2Has an optical band gap value of 4.5eV and a laser damage threshold of 80MW/cm2About the commercial material AgGaS2（5.2MW/cm2) 16 times of that of the product, and the thermal weight loss temperature is 570 ℃.
The embodiment also provides a preparation method of the mid-infrared nonlinear optical crystal material with high laser damage threshold, and the Pb is7F12Cl2The preparation method adopts a hydrothermal reaction method.
The hydrothermal reaction method in this example is to mix PbF2And NaCl is dissolved in the water solution to carry out hydrothermal reaction, thus obtaining the intermediate infrared nonlinear optical crystal material.
Preferably, the hydrothermal reaction method in this embodiment is to mix the mixture of the components in a molar ratio of 7: 2 PbF2And adding NaCl into a hydrothermal reaction kettle, adding water, sealing the reaction kettle, putting the reaction kettle into a muffle furnace, heating to 230 ℃ within 3 hours, reacting at constant temperature for 7 days, cooling to 30 ℃ at the speed of 1 ℃/h, washing a product with distilled water after cooling, performing suction filtration, and drying to obtain colorless transparent small crystals.
Furthermore, the inner lining of the reaction kettle is made of polytetrafluoroethylene.
The mid-infrared nonlinear optical crystal material Pb prepared by the embodiment7F12Cl2The relevant detection is carried out, and the test results are as follows:
(1) powder frequency doubling effect experiment:
the frequency doubling performance of the mid-infrared nonlinear optical crystal material is obtained by a Kurtz-Perry powder frequency doubling test method. The specific operation steps are as follows:
the intermediate infrared nonlinear optical crystal material prepared in example 1 was ground into powder having a particle size of about 150 to 200 μm, and then placed in a sample cell having glass windows on both sides, and the sample cell was placed on a laser light path, and a Nd: YAG pulse laser was used as a light source to generate fundamental frequency light having a wavelength of 1064nm and was injected into the sample cell, and KDP single crystal powder having a particle size of about 150 to 200 μm was used as a standard sample, and a signal was displayed on an oscilloscope via a photomultiplier. The Kurtz-Perry powder frequency doubling test result shows that the powder frequency doubling effect of the mid-infrared nonlinear optical crystal material prepared in example 1 is 2 times that of KDP. The method for testing the laser damage threshold of the powder comprises the following steps: placing sample powder to be measured between two pieces of glass, irradiating the sample with laser (1064 nm, 5ns, 1 Hz), and continuously increasing laser energy until the surface state of the sample powder changes, wherein the laser damage threshold of the measured powder is 80MW/cm2。
（2）Pb7F12Cl2Whether the frequency doubling effect is phase matching test:
the intermediate infrared nonlinear optical crystal material prepared in example 1 is ground and sieved into powders (20-40 μm, 40-60 μm, 60-80 μm, 80-100 μm, 100-125 μm, 125-150 μm and 150-200 μm) with different particle size ranges, and then the powders are respectively arranged in sample cells with glass windows on two sides, and then the sample cells are arranged on a laser light path, a Nd: YAG pulse laser is used as a light source to generate fundamental frequency light with the wavelength of 1064nm to be emitted into the sample cells, signals are displayed on an oscilloscope through a photomultiplier tube, the intensity of frequency doubling signals with different particle sizes are tested, and after drawing, the analysis judges whether the frequency doubling effect of the compound can be phase-matched.
FIG. 1 and FIG. 2 each represent Pb7F12Cl2Of crystalline [ Pb3F9Cl]4- Group configuration diagram and arrangement diagram thereof. As can be seen from the figure, Pb7F12Cl2The structure of (A) is relatively complex, each Pb atom is connected with 3F and 1 Cl to form [ PbF ]3Cl]Tetrahedra having one longer Pb-Cl bond (3.168(1) A) and three shorter Pb-F bonds (2.418(5) -2.446(2) A), such that [ PbF ] is present3Cl]The tetrahedron has a large distortion, resulting in a microscopic dipole moment, and three [ PbF ] s can be seen in the figure3Cl]The dipole moments of the tetrahedra are not completely cancelled out, and [ Pb ] is thus formed3F9Cl]4- The groups also have a microscopic dipole moment, and it can be seen from FIG. 2 that the four anionic groups, although linked to one another, are aligned in the crystal space in a substantially uniform direction, and that this alignment leads to a macroscopic dipole moment in the crystal, and thus to Pb7F12Cl2Exhibit a degree of nonlinear optical effects.
FIG. 3 shows a mid-infrared nonlinear optical crystal material Pb7F12Cl2The ultraviolet-visible absorption spectrum of the powder material of (1) can be seen from the figure, the ultraviolet absorption cut-off edge is 0.27 mu m, and the calculated band gap size is 4.5 eV.
FIG. 4 shows a mid-infrared nonlinear optical crystal material Pb prepared in example 17F12Cl2The Fourier transform attenuation infrared absorption spectrogram shows that the material does not have any absorption peak between 4000 wave numbers and 500 wave numbers, which indicates that the material has the absorption peak between 4000 wave numbers and 500 wave numbersNo absorption occurs between wave number and 500 wave number. The combination of the ultraviolet-visible absorption spectrum and the infrared spectrum shows that the material has a wide light transmission range, and the light transmission range is 0.27-20 mu m. The thermal analysis of the material and the test results of the powder frequency doubling phase matching are shown in fig. 5 and fig. 6, and as can be seen from fig. 5, the material starts thermal weight loss at a temperature of more than 570 ℃, and has good thermal stability; as can be seen from fig. 6, the material has a frequency doubling effect that can achieve phase matching that is 2 times KDP.
Example 2
The chemical formula of the mid-infrared nonlinear optical crystal material with the high laser damage threshold is Pb7F12Cl2。
The mid-infrared nonlinear optical crystal material Pb in the embodiment7F12Cl2The powder of (A) has a frequency doubling effect 2 times that of potassium dihydrogen phosphate, and has a transmission range of 0.27-20 μm.
The mid-infrared nonlinear optical crystal material Pb in the embodiment7F12Cl2Has an optical band gap value of 4.5eV and a laser damage threshold of 80MW/cm2About the commercial material AgGaS2（5.2MW/cm2) 16 times of that of the product, and the thermal weight loss temperature is 570 ℃.
The embodiment also provides a preparation method of the mid-infrared nonlinear optical crystal material with high laser damage threshold, and the Pb is7F12Cl2The preparation method adopts a solution precipitation method.
Preferably, the solution precipitation method in this embodiment is to precipitate PbF2And NaCl is added into the distilled water, heated and stirred to obtain white precipitate, and then the white precipitate is filtered, washed and dried.
Further, the solution precipitation method in the invention is to mix the solution with the solvent in a molar ratio of 7: 2 PbF2Adding NaCl and NaCl into distilled water at 75 deg.C, heating and stirring to 92 deg.C to obtain white precipitate, filtering, washing with distilled water for 2 times, and drying.
Example 3
In this embodimentInfrared nonlinear optical crystal material Pb7F12Cl2In the application of the optical fiber, the optical fiber has a wide transmission range in the middle infrared band, so the optical fiber has wide application, can be applied to the aspects of national defense, military industry, civil use and the like, and can be mainly used in the fields of optical information storage, laser communication, laser countermeasure and the like.
Claims (4)
1. The application of the mid-infrared nonlinear optical crystal material with high laser damage threshold in the optical field is characterized in that: the chemical formula of the mid-infrared nonlinear optical crystal material is Pb7F12Cl2The optical band gap value is 4.5eV, and the laser damage threshold of the powder is 80MW/cm2。
2. The application of the high laser damage threshold mid-infrared nonlinear optical crystal material in the optical field according to claim 1, is characterized in that: the Pb7F12Cl2The thermal weight loss temperature of the material is 570 ℃, and the material can be prepared by a hydrothermal reaction method or a solution precipitation method;
the solution precipitation method comprises the following steps of mixing a solution of 7: 2 PbF2Adding NaCl and NaCl into 70-80 deg.C distilled water, heating and stirring to 90-100 deg.C to obtain white precipitate, filtering, washing with distilled water for 2-3 times, and drying.
3. The application of the high laser damage threshold mid-infrared nonlinear optical crystal material in the optical field according to claim 1, is characterized in that: pb7F12Cl2The frequency doubling effect of the powder is 2 times that of potassium dihydrogen phosphate, and the transmission range is 0.27-20 mu m.
4. The application of the high laser damage threshold mid-infrared nonlinear optical crystal material in the optical field according to claim 1, is characterized in that: the hydrothermal reaction method comprises the following steps of mixing a raw material: 2 PbF2And NaCl are added into a hydrothermal reaction kettleAdding water into the lining made of polytetrafluoroethylene, sealing the reaction kettle, putting the reaction kettle into a muffle furnace, heating the reaction kettle to 230 ℃ within 3 hours, reacting at a constant temperature for 7 days, cooling the reaction kettle to 30 ℃ at the speed of 1 ℃/h, washing the product with distilled water after the temperature reduction is finished, performing suction filtration, and drying to obtain colorless transparent small crystals.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910166180.3A CN109811409B (en) | 2019-03-06 | 2019-03-06 | Mid-infrared nonlinear optical crystal material with high laser damage threshold and preparation method and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910166180.3A CN109811409B (en) | 2019-03-06 | 2019-03-06 | Mid-infrared nonlinear optical crystal material with high laser damage threshold and preparation method and application thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN109811409A CN109811409A (en) | 2019-05-28 |
| CN109811409B true CN109811409B (en) | 2021-01-05 |
Family
ID=66608280
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201910166180.3A Expired - Fee Related CN109811409B (en) | 2019-03-06 | 2019-03-06 | Mid-infrared nonlinear optical crystal material with high laser damage threshold and preparation method and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN109811409B (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2022174245A1 (en) * | 2021-02-10 | 2022-08-18 | Lawrence Livermore National Security, Llc | Innovative solutions to improve laser damage thresholds of optical structures |
| US11815705B2 (en) | 2017-06-02 | 2023-11-14 | Lawrence Livermore National Security, Llc | Innovative solutions for improving laser damage performance of multi-layer dielectric gratings |
| US11835743B2 (en) | 2017-06-02 | 2023-12-05 | Lawrence Livermore National Security, Llc | Innovative solutions to improve laser damage thresholds of optical structures |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111118600B (en) * | 2020-01-22 | 2021-09-21 | 湖北师范大学 | Mid-infrared nonlinear optical crystal material with high laser damage threshold and preparation method and application thereof |
-
2019
- 2019-03-06 CN CN201910166180.3A patent/CN109811409B/en not_active Expired - Fee Related
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US11815705B2 (en) | 2017-06-02 | 2023-11-14 | Lawrence Livermore National Security, Llc | Innovative solutions for improving laser damage performance of multi-layer dielectric gratings |
| US11835743B2 (en) | 2017-06-02 | 2023-12-05 | Lawrence Livermore National Security, Llc | Innovative solutions to improve laser damage thresholds of optical structures |
| WO2022174245A1 (en) * | 2021-02-10 | 2022-08-18 | Lawrence Livermore National Security, Llc | Innovative solutions to improve laser damage thresholds of optical structures |
Also Published As
| Publication number | Publication date |
|---|---|
| CN109811409A (en) | 2019-05-28 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN109811409B (en) | Mid-infrared nonlinear optical crystal material with high laser damage threshold and preparation method and application thereof | |
| CN111719182B (en) | Europium iodate monohydrate infrared nonlinear optical crystal material and preparation and application thereof | |
| Kumar et al. | Growth, linear and nonlinear optical and, laser damage threshold studies of organometallic crystal of MnHg (SCN) 4 | |
| WO2017132815A1 (en) | Infrared nonlinear optical crystals, preparation method therefor, and applications thereof | |
| CN106757344B (en) | Two kinds of inorganic fluoriodate crystal and its preparation method and application | |
| CN103789831B (en) | Non-linear optical crystal of iodic acid bismuth rubidium and its preparation method and application | |
| CN109706523B (en) | Intermediate infrared nonlinear optical crystal material and preparation method and application thereof | |
| CN109137072B (en) | Inorganic nonlinear optical crystal sodium bismuth iodate and preparation and application thereof | |
| CN102296364B (en) | Inorganic infrared non-linear optical crystal material and preparation method thereof | |
| CN117987918A (en) | Organic-inorganic hybrid antimony-based oxyfluoride second-order nonlinear optical crystal material, preparation and application thereof | |
| CN103774223B (en) | Infrared nonlinear optical crystal material Rb in one 2cdBr 2i 2and preparation method thereof | |
| US4756598A (en) | Second harmonic generation with 5-chloro-2-nitroaniline | |
| CN102560648B (en) | Infrared non-linear optic crystalline material and preparation method thereof | |
| CN115216844B (en) | Preparation and application of middle-far infrared nonlinear optical crystal cadmium sulfide phosphate | |
| CN100362145C (en) | Non-linear optics crystal material, process for preparing the same and purposes thereof | |
| CN111118600B (en) | Mid-infrared nonlinear optical crystal material with high laser damage threshold and preparation method and application thereof | |
| CN101311353A (en) | Second order nonlinear optical crystal material, preparation method and use thereof | |
| CN115961353A (en) | Medium-far infrared nonlinear optical crystal sulfur germanium silver, preparation method and application | |
| CN113235160B (en) | Cerium fluoroiodate second-order nonlinear optical crystal material and preparation and application thereof | |
| CN111850689A (en) | Fluorine-substituted mixed metal salt nonlinear optical crystal material and preparation and application thereof | |
| CN113417008A (en) | Second-order nonlinear optical crystal of cerium iodate and sulfate and preparation and application thereof | |
| CN104962992A (en) | Middle-infrared nonlinear optical crystal material KBi4F13, and preparation method and application thereof | |
| CN103073050A (en) | Application of mercuric iodobromide as infrared band second-order nonlinear optical material | |
| CN113481600B (en) | Second-order nonlinear optical crystal material of cerium iodate and phosphate, preparation method thereof and application thereof in laser frequency conversion | |
| CN115896951B (en) | Mixed halogen lead acetate second-order nonlinear optical crystal and preparation method and application thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20210105 |
|
| CF01 | Termination of patent right due to non-payment of annual fee |