CN100576050C - The mercuric bromide crystal is as the application of infrared band nonlinear optical material - Google Patents
The mercuric bromide crystal is as the application of infrared band nonlinear optical material Download PDFInfo
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- CN100576050C CN100576050C CN200810048261A CN200810048261A CN100576050C CN 100576050 C CN100576050 C CN 100576050C CN 200810048261 A CN200810048261 A CN 200810048261A CN 200810048261 A CN200810048261 A CN 200810048261A CN 100576050 C CN100576050 C CN 100576050C
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Abstract
The present invention relates to of the application of mercuric bromide crystal as the infrared band nonlinear optical material.HgBr
2The crystal powder frequency-doubled effect is about 10 * KDP, and can phase matching; In 400-800 nanometer (being visible region) and 2.5-25 micron (being the service band of mid-infrared light spectrometer) full impregnated mistake; Laser damage threshold can reach 0.3GW/cm
2More than, these data hold a safe lead in existing infrared non-linear optical material, than having the highest numerical value (LiInS that known report is crossed now
20.1GW/cm
2) be significantly improved; Can be used as outstanding infrared band nonlinear optical crystal, and be particularly suitable for the application of high power laser light frequency inverted aspect.
Description
Technical field
This patent relates to the application of mercuric bromide crystal as the infrared band nonlinear optical material, belongs to material science and optical field.
Background technology
The second nonlinear crystalline material has important use in fields such as laser frequency conversion, optical parametric oscillation, optical parameter amplifications, and national economy, national defense and military are had significant values.The wave band classification of second-order non-linear optical materials from using is divided into three kinds of ultraviolet, visible near-infrared, infrared bands.Its medium ultraviolet and visible near-infrared wave band have been invented/have been showed and satisfied several outstanding materials that practicability requires fully, and infrared band lacks the outstanding nonlinear optical material of practicability.The material of existing commercialization infrared band is such as AgGaS
2, AgGaSe
2Deng, though have bigger nonlinear optical coefficients, good phase matching character, outstanding physics and chemical stability, their laser damage threshold is lower, has influenced their uses in directions such as laser frequency conversions.The novel second-order non-linear optical materials that can be applied to infrared band that invention/existing is a kind of to have high laser damage threshold and kept the major advantage of traditional material haply has the meaning of particular importance.
Point out that outstanding infrared non-linear optical material should possess following feature in " non-linear optical crystal material science " book (Science Press's publication) by the Zhang Kecong chief editor.Bigger nonlinear optical coefficients, can realize phase matching, good physics and chemical stability, at transparent, the higher laser damage threshold of service band.The crystalline material that satisfies above condition just can become the material of practicability.
Summary of the invention
The present invention provides a kind of infrared band nonlinear optical material at the problems referred to above exactly, this nonlinear optical material not only has bigger nonlinear optical coefficients, can realize phase matching, good physics and chemical stability, transparent at service band, and has higher laser damage threshold.
Technical scheme provided by the invention is: the mercuric bromide crystal is as the application of infrared band nonlinear optical material.
Preferably, mercuric bromide crystal of the present invention is as the application of infrared band laser frequency inverted material.
More preferably, mercuric bromide crystal of the present invention is as the application of infrared band high power laser light frequency inverted material.
The laser damage threshold of above-mentioned mercuric bromide crystal is not less than 0.3GW/cm
2
The mercuric bromide raw material of above-mentioned mercuric bromide crystal of growing need be removed wherein impurity through recrystallization in distillation and the aqueous solution.
The applicant discovers HgBr
2The crystal powder frequency-doubled effect is about 10 * KDP, and can phase matching; In 400-800 nanometer (being visible region) and 2.5-25 micron (being the service band of mid-infrared light spectrometer) full impregnated mistake.Laser damage threshold can reach 0.3GW/cm
2More than, these data hold a safe lead in existing infrared non-linear optical material, than having the highest numerical value (LiInS that known report is crossed now
20.1GW/cm
2) be significantly improved.
In addition, the analytically pure mercuric bromide reagent that buys usually uses conventional method purifying (recrystallization in distillation or the alcohol), all can not avoid its middle infrared spectrum 450cm
-1The not clear absorption occur at the place, we are by discovering for a long time, and these absorptions are owing to contain micro-HgCl in the raw material
2, CdCl
2, CdBr
2Cause Deng impurity.These impurity meeting planar water perhaps form the salt that contains water of crystallization with water, have influenced the through performance of mercuric bromide at the correspondence position of middle infrared spectral region.The method of recrystallization can not effectively be removed impurity in distillation and the alcoholic solution.The applicant adopts distillation to add from aqueous solution the method for recrystallization repeatedly, has reached the purpose of removing these impurity.
Based on above-mentioned HgBr
2The a series of outstanding physicochemical property of crystal have determined it must can be used as the infrared band nonlinear optical material, further can be used as infrared band high power laser light frequency inverted material.
Description of drawings
Fig. 1 mercuric bromide powder frequency multiplication phase matching curve;
Fig. 2 mercuric bromide ultraviolet-visible absorption spectroscopy;
Fig. 3 mercuric bromide thermogravimetric spectrogram;
Mercuric bromide infrared permeation spectrogram behind Fig. 4 process this patent purifying;
Fig. 5 mercuric bromide infrared spectrum that (usual way) purified that only distils.
Embodiment
Be further described below in conjunction with the technical scheme of concrete experimental data this patent:
The purifying of embodiment 1. mercuric bromide samples
Take by weighing the pure mercuric bromide sample of commercially available analysis 4 grams, place the distillation device to distil, after distillation finishes, collect the product after distillation is purified, use 150ml distilled water, heating for dissolving it.Filtered while hot then, the filtrate crystallisation by cooling.Filter, with the gained solid repeatedly the water recrystallization just can remove wherein impurity such as Cd salt.Chilling temperature is low more, and the recrystallization yield is high more.
Infrared, the ultraviolet-visual spectrum of embodiment 2. mercuric bromide samples, thermogravimetric analysis and ambient stable property testing
Infrared spectrum carries out on Omnic Nicolet 5700 spectrometers, wherein the lobate LED reverse mounting type that obtains behind the aqueous solution recrystallization directly is used for testing the middle infrared spectrum of mercuric bromide, the result as shown in Figure 4, mercuric bromide (does not have tangible absorption peak, illustrates that this crystal has the good attribute that sees through at infrared band in whole middle infrared spectral region in 2.5～25um) scopes.The sample of aqueous solution recrystallization of no use (only distillation handle) then is to test the spectrogram that obtains with pressing potassium bromide troche, and the result can see 3400,1600,400～500cm as shown in Figure 5
-1Near absorption peak appears respectively, these absorption peak peak shapes are sharp-pointed, and are bimodal about 3400, judge thus, these absorption peaks are because water of crystallization causes.In conjunction with Fig. 4, illustrate that our purifying has played the effect of removing miscellaneous affair and improving the material infrared permeation really.
Uv-vis spectra is the HgBr that tests on Varian Cary 5000 spectrometers
2The powder absorption spectra.Thermogravimetric analysis then has been to use the Diamond DTA/TG analyser of a Perkin Elmer company, obtains under nitrogen atmosphere.
From Fig. 2, the ultraviolet absorption edge of mercuric bromide appears at 378nm, and the bandwidth of corresponding level structure is about 3.3eV, and is more high such as S-Ga-Ag than traditional infrared non-linear optical material.Bandwidth is high more, and laser damage threshold is big more.In fact the test of back also proves, mercuric bromide has higher laser damage threshold.And mercuric bromide does not absorb at visible region, illustrates that it also can be applied to visible region.
From Fig. 3.Mercuric bromide illustrates that obviously not weightless below 100 ℃ it is at the following good thermal stability of this temperature.
We once will be through behind the purifying, and the crystal of cultivating from solution then exposes to the sun and leaked in air and sunlight 90 days, does not observe the variation of crystal morphology.Illustrate that crystal has stability preferably to environment.
The powder frequency multiplication test of embodiment 3. mercuric bromides
The frequency doubling property of material obtains by Kurtz powder frequency multiplication method of testing.The concrete operations step is as follows:
With raw material through recrystallization purifying in distillation and the aqueous solution, and then in ethanol the HgBr of crystallization gained
2Crystal, at first grind to form the powder of the about 0.08～0.10mm granularity of diameter, being contained in the two sides then has in the sample cell of windowpane, afterwards sample cell is placed on the laser optical path, using the Nd:YAG pulsed laser to produce wavelength as light source is that the fundamental frequency light of 1064 nanometers is injected sample cell, and signal detects and amplifies through photomultiplier and is shown on the oscillograph.Be that standard specimen contrasts with unidimensional KDP and KTP sample then.The intensity of its powder SHG signal is about 10 times or 0.8 times of KTP of KDP.
The phase matching test of embodiment 4. mercuric bromides
Crystal among the embodiment 3 is ground and sieves into the powder (0.04-0.05,0.05-0.06,0.06-0.08,0.08-0.10,0.10-0.125,0.125-0.15,0.15-0.2 millimeter) of different grain size scope at first respectively, being contained in the two sides then has in the sample cell of windowpane, afterwards sample cell is placed on the laser optical path, using the Nd:YAG pulsed laser to produce wavelength as light source is that the fundamental frequency light of 1064 nanometers is injected sample cell, and signal detects and amplifies through photomultiplier and is shown on the oscillograph.
Fig. 1 is a test result, and from figure, the powder frequency multiplication intensity of mercuric bromide increases along with the increase of grain graininess, during to particle diameter 0.125mm, reaches maximal value substantially.Pertinent literature statement according to Kurtz powder method test crystal powder frequency-doubled effect.This is the powder frequency multiplication-grading curve that typically can realize the second-order non-linear optical materials of phase matching.The second nonlinear optic character that has fully proved mercuric bromide can realize phase matching.
The test of embodiment 5. laser damage thresholds
A transparent crystal that grows out has been used in the test of laser damage threshold from ethanolic solution, crystal is not through handling (such as plated film, polishing or the like) any early stage.What laser instrument adopted is the Nd:YAG pulsed laser of a 5Hz, and emission wavelength is the laser of 1064 nanometers, and the energy of each pulse is approximately 0.4J, and half pulsewidth is 8ns, the about 5mm of beam diameter, and the power density of each pulse is about 0.18GW/cm
2Convex lens are used to converge laser beam, in order to adjust the diameter of illuminating area, obtain the intensity of illumination of different capacity density.Crystal to be measured is fixed on 1000 pulses of bearing on the position under each power density (intensity), and with the variation of crystal outward appearance before and after the microscopic examination illumination that has camera, intensity constantly enhancing is damaged until crystal.
After the absorption of all components and parts on the deduction light path, the data that record are 0.3GW/cm
2Than having the highest numerical value LiInS that known report is crossed now
2Numerical value 0.1GW/cm under approximate test condition
2Exceed 2 times.Embodied the high resisting laser damage ability of mercuric bromide crystal.
Comprehensive above case, mercuric bromide crystal laser damage threshold valve height; See through wide ranges at visible region and infrared light district; Nonlinear optical response bigger and can phase matching is arranged; Airborne water and oxygen had advantages of higher stability.It can be used as outstanding infrared band nonlinear optical crystal, and is particularly suitable for the application of high power laser light frequency inverted aspect.
Claims (4)
1. the mercuric bromide crystal is as the application of infrared band nonlinear optical material.
2. application according to claim 1 is characterized in that: described infrared band nonlinear optical material is an infrared band laser frequency inverted material.
3. application according to claim 2 is characterized in that: the laser damage threshold of above-mentioned mercuric bromide crystal is not less than 0.3GW/cm
2
4. according to claim 1 or 2 or 3 described application, it is characterized in that: the mercuric bromide raw material of the above-mentioned mercuric bromide crystal of growing need be removed wherein impurity through recrystallization in distillation and the aqueous solution.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN103073050A (en) * | 2013-01-18 | 2013-05-01 | 武汉大学 | Application of mercuric iodobromide as infrared band second-order nonlinear optical material |
| CN105970282B (en) * | 2016-05-20 | 2018-12-18 | 武汉科技大学 | A kind of FTIR radiation transmittance and its preparation method and application |
| CN105951182A (en) * | 2016-05-23 | 2016-09-21 | 中国科学院福建物质结构研究所 | Infrared nonlinear optical crystal material, method for preparing same and application of infrared nonlinear optical crystal material |
| CN106835284A (en) * | 2017-01-18 | 2017-06-13 | 中国科学院福建物质结构研究所 | One class infrared nonlinear optical crystal material and its production and use |
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Non-Patent Citations (6)
| Title |
|---|
| Mercury bromide(HgBr2): A promising nonlinearopticalmaterial in IR region with a high laser damage threshold. Liu.T et.al.APPLIED PHYSICS LETTERS,Vol.93 No.9. 2008 |
| Mercury bromide(HgBr2): A promising nonlinearopticalmaterial in IR region with a high laser damage threshold. Liu.T et.al.APPLIED PHYSICS LETTERS,Vol.93 No.9. 2008 * |
| 新型非线性光学晶体台阶动力学与生长机理：ATMB. 于锡玲等.人工晶体学报，第27卷第3期. 1998 |
| 新型非线性光学晶体台阶动力学与生长机理：ATMB. 于锡玲等.人工晶体学报，第27卷第3期. 1998 * |
| 溴化汞激光泵浦的可调谐染料激光器. 张翼翔等.激光与红外，第3期. 1984 |
| 溴化汞激光泵浦的可调谐染料激光器. 张翼翔等.激光与红外，第3期. 1984 * |
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