CN102560648B - Infrared non-linear optic crystalline material and preparation method thereof - Google Patents
Infrared non-linear optic crystalline material and preparation method thereof Download PDFInfo
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- CN102560648B CN102560648B CN201210064873.XA CN201210064873A CN102560648B CN 102560648 B CN102560648 B CN 102560648B CN 201210064873 A CN201210064873 A CN 201210064873A CN 102560648 B CN102560648 B CN 102560648B
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- infrared
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Abstract
The invention discloses an infrared non-linear optic crystalline material, wherein the infrared non-linear optic crystalline material has a molecular formula of Cs2HgCl12I2 and a crystal space group of P21. The CsCl and the HgI2 are taken as initial reactants and a solid-phase tube-sealing method and an organic solvent method are respectively used for preparing the material. The infrared non-linear optic crystalline material has a strong phase-matched second-order non-linear optic effect, is provided with huge light-permeable windows in a visible light area and an infrared light area, and has the advantages of higher laser damage threshold, heat stability; and a synthesizing method is simple to operate, reaction time is short, experiment conditions are mild, and the product has high purity and can be widely applied to the optical field.
Description
Technical field
The present invention relates to a kind of preparation of novel inorganic compound and the application as non-linear optical crystal material thereof, belong to domain of inorganic chemistry, also belong to material science and optical field.
Background technology
Non-linear optical effect originates from the interaction of laser and medium.When laser is when having the Propagation of non-zero second order susceptibility, the non-linear optical effect such as frequency multiplication and frequency, difference frequency, optically erasing can be produced.Utilize the second order nonlinear optical effect of crystal, the device for non-linear optical such as second harmonic generator, frequency converter, optical parametric oscillator can be made, in a lot of fields, as aspects such as laser technology, atmospheric surveillance, national defense and military, important using value is had.Inorganic Nonlinear Optical Materials occupies dominant position in the practical research of second-order non-linear optical materials.According to transmission region and the scope of application, inorganic nonlinear optical crystal material can be divided into ultraviolet region nonlinear optical material, visible region nonlinear optical material and infrared light district nonlinear optical material.The Inorganic Nonlinear Optical Materials having dropped into practical ultraviolet and visible region at present has BBO (beta-barium metaborate), LBO (lithium tetraborate), KDP (potassium primary phosphate), KTP (potassium titanium oxide phosphate) etc., substantially can meet the requirement of most of practicality.But for FTIR radiation transmittance, also have gap from practicality.Reason is existing FTIR radiation transmittance, as AgGaS
2, AgGaSe
2deng, although have very large nonlinear second-order optical susceptibility, also have very wide through scope in infrared light district, but synthesis condition is harsh, be not easy to grow up to the high monocrystalline of large optical quality, particularly damage threshold is lower, thus can not meet the practical requirement of non-linear optical crystal material.And the frequency inverted realizing infrared laser has important value in the field such as national economy, national defence, as realized continuously adjustable molecular spectrum, realize 3 ~ 5 micron waveband continuous laser spectrum etc.Thus the research of infrared inorganic nonlinear optical material has become an important topic of current nonlinear optical material research field.In " non-linear optical crystal material science " book of Science Press's publication in 2003, clearly " in the spectral band of whole nonlinear optics; the non-linear optic crystal of infrared band is a weak link; therefore, have to be strengthened to the research of the novel frequency conversion crystal of this wave band " is proposed.
Summary of the invention
Problem to be solved by this invention is to provide a kind of easily preparation and good inorganic infrared nonlinear optical crystal material of stability and preparation method thereof.
Technical scheme provided by the invention is:
A kind of infrared nonlinear optical crystal material, its molecular formula is Cs
2hgCl
2i
2, crystal space group is P2
1.
Above-mentioned infrared nonlinear optical crystal material powder SHG effect is 1.0 × KTP; Realize phase matched; Full impregnated overrange is 0.5 ~ 25 micron; The laser damage threshold of crystal is 70MW/cm
2; Thermal weight loss temperature is 220 DEG C.
The preparation method of above-mentioned inorganic infrared nonlinear optical crystal material:
By CsCl and HgI
2by the molar ratio weighing of 2: 1, in agate mortar after grinding evenly, load in ampoul tube, vacuumize rear tube sealing; Then be placed in muffle furnace to react, be warming up to 200-300 DEG C and constant temperature 10-24 hour, then be cooled to 100-200 DEG C, constant temperature is cooled to room temperature after 5 hours again, obtain yellow crystalline product after reaction terminates, reaction product is added suction filtration after a small amount of dehydrated alcohol rinse, obtain yellow product.
The speed being warming up to 200-300 DEG C can be 1 DEG C/min.
Another preparation method of above-mentioned inorganic infrared nonlinear optical crystal material is:
By CsCl and HgI
2molar ratio weighing by 2: 1 is also dissolved in organic solvent, and stirred at ambient temperature or heating, be obtained by reacting light yellow settled solution, filters after leaving standstill, and under filtrate being placed in water bath with thermostatic control or room temperature, volatilization obtains cubic clear, yellowish crystal.
Above-mentioned organic solvent is acetone, ethanol, acetonitrile, tetrahydrofuran (THF) or ethyl acetate etc.
Below the reaction equation preparing compound of the present invention:
2CsCl+HgI
2→Cs
2HgCl
2I
2
Inorganic FTIR radiation transmittance Cs disclosed in this invention
2hgCl
2i
2with [HgCl
2i
2] as anionic group, A position positively charged ion is alkalimetal ion Cs
+.Accompanying drawing 1 and Fig. 2 are infrared nonlinear optical crystal material (Cs of the present invention
2hgCl
2i
2) crystal accumulation figure, can see the anionic group of this kind of compound be distortion [HgCl
2i
2] tetrahedral configuration, and the direction of distortion is basically identical, thus be conducive to the geometric superposition of microcosmic second order nonlinear optical effect.The spacer of this crystalline material is P2
1, unit cell parameters is a=8.0066 (9),
α=90 °, β=108.152 (1) °, γ=90 °.This compound containing crystal water, does not absorb in whole mid-infrared light district; In visible region, ABSORPTION EDGE observed value reaches 0.5 micron.There is stronger non-linear optical effect and laser damage threshold.In a word, it has excellent over-all properties, can be used as non-linear optical crystal material and is applied.
This novel inorganic infrared nonlinear optical crystal material that the present invention obtains has following characteristics:
1. have larger frequency-doubled effect (SHG), Kurtz powder frequency doubling test result shows that its powder SHG effect is suitable with potassium titanium oxide phosphate (KTP);
2. compound has very wide through scope in visible region and infrared light district, is 0.5 ~ 25 micron completely through wave band;
3. not containing crystal water, to air-stable, not deliquescence, and better heat stability;
4. compound can realize phase matched;
5. simple solvent evaporation method can be utilized to prepare.
Accompanying drawing explanation
Fig. 1 is Cs of the present invention
2hgCl
2i
2crystal accumulation figure;
Fig. 2 is Cs of the present invention
2hgCl
2i
2[the HgCl of middle distortion
2i
2] tetrahedral configuration;
Fig. 3 is Cs of the present invention
2hgCl
2i
2uV-visible-near infrared absorption;
Fig. 4 is Cs of the present invention
2hgCl
2i
2infrared through spectrum, IR (2.5 ~ 25 microns) spectrum;
Fig. 5 is Cs of the present invention
2hgCl
2i
2thermal weight loss collection of illustrative plates;
Fig. 6 is Cs of the present invention
2hgCl
2i
2phase matched collection of illustrative plates.
Embodiment
Below in conjunction with specific embodiment, technical scheme of the present invention is further described:
Embodiment 1:Cs
2hgCl
2i
2preparation
Solid phase tube sealing synthesis method: by 1.6836 grams of cesium chlorides (CsCl, 10mmol) and 2.2745 grams of red mercury iodide (HgI
2, 5mmol) after grinding evenly, load in heavy wall ampoul tube in agate mortar; Be evacuated to 10
-2below Pa, with alcohol blast burner flame tube sealing; Then be placed in muffle furnace, be slowly warming up to 200-300 DEG C and constant temperature 10-24 hour with the speed of 1 DEG C/min, then be cooled to 100-200 DEG C, after constant temperature 1-10 hour, be cooled to room temperature again.Yellow crystalline product is obtained after reaction terminates.Reaction product is filtered with after a small amount of dehydrated alcohol rinse, obtains yellow product.
Embodiment 2:Cs
2hgCl
2i
2preparation
Solution synthetic method: by 1.6836 grams of (10mmol) CsCl and 2.2745 grams of (5mmol) HgI
2be added in flask, add 20ml acetone, also thermal response a few hours obtain light yellow settled solution to room temperature rapid stirring a little.Filter after leaving standstill, water bath with thermostatic control volatilization filtrate being placed in 20 ~ 50 DEG C can obtain cubic clear, yellowish crystal.
Embodiment 3:Cs
2hgCl
2i
2crystal growth
By CsCl and HgI
2be dissolved in 20 milliliters of acetone, wherein CsCl and HgI simultaneously
2consumption mol ratio be 2: 1.Obtain yellow clear solution about stirring half an hour, filter, filtrate is placed in the thermostatic bath evaporation of 20 ~ 50 degrees Celsius after 5 ~ 30 days, the cubic clear, yellowish monocrystalline growing up to large-size is required crystalline material.
Embodiment 4:Cs
2hgCl
2i
2crystal growth
By CsCl and HgI
2be dissolved in the tetrahydrofuran (THF) of 20 milliliters, wherein CsCl and HgI simultaneously
2consumption mol ratio be 2: 1.Stir and obtain yellow clear solution in 10-60 minute, filter, filtrate is placed in the thermostatic bath evaporation of 20 ~ 50 degrees Celsius after 5 ~ 30 days, the cubic clear, yellowish monocrystalline growing up to large-size is required crystalline material.
Embodiment 5:Cs
2hgCl
2i
2powder SHG effect
The frequency doubling property of material is obtained by Kurtz powder frequency doubling testing method.Concrete operation step is as follows:
First the second-order non-linear optical crystal material of gained is ground the powder into about 100 micron granularities, then being contained in two sides has in the sample pool of glass port, afterwards sample pool is placed on laser optical path, the fundamental frequency light that use Nd:YAG pulsed laser is 1064 nanometers for light source generation wavelength injects sample pool, using the KTP monocrystal of about 100 micron granularities as standard specimen, signal is shown on oscilloscope through photomultiplier.
Embodiment 6:Cs
2hgCl
2i
2phase matched is tested
The second-order non-linear optical crystal material of gained is ground first respectively and is sieved into the powder (40 ~ 60 of different grain size scope, 60 ~ 80,80 ~ 100,100 ~ 125,125 ~ 150,150 ~ 200 microns), then being contained in two sides has in the sample pool of glass port, afterwards sample pool is placed on laser optical path, the fundamental frequency light that use Nd:YAG pulsed laser is 1064 nanometers for light source generation wavelength injects sample pool, using the KTP monocrystal of about 100 micron granularities as standard specimen, signal is shown on oscilloscope through photomultiplier.
Gained compound measures through x-ray crystal structure, and its crystal structure arrangement is shown in Fig. 1.Product is through ultraviolet-visible-near infrared spectrum, and infrared spectra, the test result of thermal analyses and phase matched, is shown in Fig. 3,4,5 and 6.Material reaches 0.5 micron in the ABSORPTION EDGE of visible region; Do not absorb in whole mid-infrared light district, there is larger transparency range; Material just starts weightlessness at 220 degrees Celsius later, has good thermostability; As seen from Figure 6, material can phase matched.
Cs
2hgCl
2i
2the laser damage threshold test of crystal adopts band to adjust the Nd:YAG pulsed laser of Q, crystal being directly placed in laser facula place, whether having the changes such as visible color, transparency, profile to observing crystal after same position Continuous irradiation 300 pulses of crystal.Position again by changing lens regulates spot size successively, observes laser radiation and crystal is changed, judge the laser damage threshold of crystal.The optical source wavelength of laser apparatus is 1064nm, and half pulsewidth is 8ns, and the average energy of each pulse is about 400mJ, and spot diameter is initially 6mm, and (facula area is 28.26mm
2, the transmitance of initial laser energy decrement sheet is 77.1%) time, calculating its average power density is 0.14GW/cm
2.Under the prerequisite that pulsed laser energy is identical, the average power density of laser and the area of hot spot are inversely proportional to.So mean power when laser facula area is initial area 2 times is 0.14 × 1/2GW/cm
2=0.07GW/cm
2=70MW/cm
2, the rest may be inferred).When we regulate facula area to be 4 times of initial facula area, there is not any obvious change in crystal; Regulate facula area to be 2 times of initial area again, after irradiating 300 pulses, crystal does not observe obvious damage phenomenon yet.Now the mean power of laser is 70MW/cm
2, when regulating facula area to be 1.5 times of initial area further, after irradiating 300 pulses, crystal has obvious damage.Therefore, we think Cs
2hgCl
2i
2the laser damage threshold of crystal is 70MW/cm
2.Accompanying drawing 1 and Fig. 2 are infrared nonlinear optical crystal material (Cs of the present invention
2hgCl
2i
2) crystal accumulation figure, can see the anionic group of this kind of compound be distortion [HgCl
2i
2] tetrahedral configuration, and the direction of distortion is basically identical, thus be conducive to the geometric superposition of microcosmic second order nonlinear optical effect.The spacer of this crystalline material is P2
1, unit cell parameters is a=8.0066 (9),
α=90 °, β=108.152 (1) °, γ=90 °.This compound containing crystal water, does not absorb in whole mid-infrared light district; In visible region, ABSORPTION EDGE observed value reaches 0.5 micron.
Claims (3)
1. an infrared nonlinear optical crystal material, its molecular formula is Cs
2hgCl
2i
2, crystal space group is P2
1, unit cell parameters is a=8.0066 (9)
,
α=90 °, β=108.152 (1) °, γ=90 °.
2. the preparation method of infrared nonlinear optical crystal material described in claim 1, is characterized in that:
By CsCl and HgI
2by the molar ratio weighing of 2: 1, in agate mortar after grinding evenly, load in ampoul tube, vacuumize rear tube sealing; Then be placed in muffle furnace to react, be warming up to 200-300 DEG C and constant temperature 10-24 hour, then be cooled to 100-200 DEG C, constant temperature is cooled to room temperature after 5 hours again; Obtain yellow crystalline product after reaction terminates, reaction product is added suction filtration after dehydrated alcohol rinse, obtain yellow product.
3. preparation method according to claim 2, is characterized in that, the speed being warming up to 200-300 DEG C is 1 DEG C/min.
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| CN103757697B (en) * | 2014-01-24 | 2015-10-21 | 武汉大学 | A kind of Inorganic crystal compound and its preparation method and application |
| CN103774223B (en) * | 2014-02-26 | 2016-03-16 | 武汉大学 | Infrared nonlinear optical crystal material Rb in one 2cdBr 2i 2and preparation method thereof |
| CN105483826B (en) * | 2016-01-19 | 2018-12-18 | 武汉科技大学 | Application of the one water potassium triiodomercurate crystal in second nonlinear optic field |
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| SU1839797A1 (en) * | 1979-01-26 | 2005-05-27 | Кубанский государственный университет | Method for production of mercury thiogallate single crystals |
| CN1737217A (en) * | 2005-08-16 | 2006-02-22 | 武汉大学 | Non-linear optics crystal material, process for preparing the same and purposes thereof |
| CN101216656A (en) * | 2008-01-14 | 2008-07-09 | 武汉大学 | Inorganic infrared nonlinear optical crystal material and method for making same and uses |
| RU2344208C1 (en) * | 2007-05-28 | 2009-01-20 | Институт геологии и минералогии Сибирского отделения Российской академии наук (ИГМ СО РАН) | Nonlinear mono-crystal lithium chalkogenides |
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| CN1038352C (en) * | 1994-04-15 | 1998-05-13 | 中国科学院福建物质结构研究所 | Non-linear optical crystal strontium boroberyllate |
| US8038904B2 (en) * | 2004-04-14 | 2011-10-18 | Deep Photonics Corporation | Method and structure for non-linear optics |
| CN101024899B (en) * | 2006-02-21 | 2012-07-18 | 中国科学院福建物质结构研究所 | Non-linear optical crystal selenium borate |
| CN101545141B (en) * | 2008-03-25 | 2013-04-17 | 中国科学院福建物质结构研究所 | Gallium and barium sulfide monocrystal as well as growing method and infrared nonlinear optical device thereof |
| CN102191554B (en) * | 2010-03-02 | 2015-06-17 | 中国科学院福建物质结构研究所 | Infrared non-linear optical crystals Ln4GaSbS9 |
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2012
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Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| SU1839797A1 (en) * | 1979-01-26 | 2005-05-27 | Кубанский государственный университет | Method for production of mercury thiogallate single crystals |
| CN1737217A (en) * | 2005-08-16 | 2006-02-22 | 武汉大学 | Non-linear optics crystal material, process for preparing the same and purposes thereof |
| RU2344208C1 (en) * | 2007-05-28 | 2009-01-20 | Институт геологии и минералогии Сибирского отделения Российской академии наук (ИГМ СО РАН) | Nonlinear mono-crystal lithium chalkogenides |
| CN101216656A (en) * | 2008-01-14 | 2008-07-09 | 武汉大学 | Inorganic infrared nonlinear optical crystal material and method for making same and uses |
| CN102296364A (en) * | 2011-09-15 | 2011-12-28 | 武汉大学 | Inorganic infrared non-linear optical crystal material and preparation method thereof |
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