CN107557867B - Sulphur tin zinc sodium and sulphur tin zinc sodium mid and far infrared nonlinear optical crystal and preparation method and application - Google Patents
Sulphur tin zinc sodium and sulphur tin zinc sodium mid and far infrared nonlinear optical crystal and preparation method and application Download PDFInfo
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- CN107557867B CN107557867B CN201610516154.5A CN201610516154A CN107557867B CN 107557867 B CN107557867 B CN 107557867B CN 201610516154 A CN201610516154 A CN 201610516154A CN 107557867 B CN107557867 B CN 107557867B
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Abstract
The present invention relates to a kind of sulphur tin zinc sodium and sulphur tin zinc sodium mid and far infrared nonlinear optical crystal and preparation method and application, the chemical formula of the compound is Na2ZnSn2S6, molecular weight 541.09 is crystal grain.The chemical formula of the crystal is Na2ZnSn2S6, it is rhombic system that molecular weight 541.09, which is non-centrosymmetric structure, space group is Fdd2, and cell parameter is a=12.945(3), b=23.556(5), c=7.2774(15), α=β=γ=90 °, Z=8, unit-cell volume V=2219.1(8)3；Using by SODIUM METAL, simple substance zinc, the solid phase reaction of simple substance tin and elemental sulfur under vacuum conditions；The powder xrd pattern and theoretical calculation of sulphur tin zinc sodium and sulphur tin zinc sodium mid and far infrared nonlinear optical crystal of the present invention；Under the laser irradiation of 2090nm, granularity is 0.105-0.15 μm of Na2ZnSn2S6Frequency-doubled effect is commercialized S-Ga-Ag (AgGaS2) 4 times.
Description
Technical field
The invention belongs to infrared nonlinear optical crystal material fields, and in particular to a kind of compound sulphur tin zinc sodium and sulphur tin
Zinc sodium mid and far infrared nonlinear optical crystal and preparation method and application
Background technique
Non-linear optical crystal material can be classified as three categories according to its range through wave band: one, ultraviolet and dark purple
Wave section nonlinear optical material；Two, visible light and near infrared band nonlinear optical material；Three, infrared and mid and far infrared is non-
Linear optical material.Work of the invention belongs to visible light and mid and far infrared nonlinear optical material.The nonlinear optical of the wave band
Crystal color material tool is learned to have been widely used, such as see in laser frequency converter, coherent infrared radar, laser communications, infrared filtering device,
The application of photoelectronic warfare etc..
Up to the present, the generation of 3-20 μm of solid-state mid and far infrared wave band of laser is based primarily upon nonlinear optics principle and red
Outer nonlinear optical crystal converter technique and obtain.In the market, common infrared non-linear optics is brilliant for infrared nonlinear optical crystal
Body mainly has AgGaS2, AgGaSe2, ZnGeP2Deng.Although these crystal are all in civilian production life high-tech area and military affairs
It is acted in equipment, but the shortcomings that these crystalline materials also have itself, and people's reason is also unable to reach in comprehensive performance
The requirement thought, with the development of technology with desired raising, the demand to more excellent performance of infrared non-linear crystal is more
It is urgent, therefore the exploration for novel mid and far infrared nonlinear crystal, in civilian high-tech industry and in terms of promoting military equipment
All there is important strategic importance, and crystalline material synthesis and growth are a kind of huge challenges of the direction.
Summary of the invention
The object of the present invention is to provide a kind of sulphur tin zinc sodium and sulphur tin zinc sodium mid and far infrared nonlinear optical crystal and systems
Preparation Method and application, the chemical formula of the compound are Na2ZnSn2S6, molecular weight 541.09 is polycrystal powder.The chemistry of the crystal
Formula is Na2ZnSn2S6, it is rhombic system, space group Fdd2, cell parameter that molecular weight 541.09, which is non-centrosymmetric structure,
Forα=β=γ=90 °, Z=8, unit cell body
ProductUsing by SODIUM METAL, simple substance zinc, the solid phase reaction of simple substance tin and elemental sulfur under vacuum conditions；This
The powder xrd pattern and theoretical calculation of invention sulphur tin zinc sodium and sulphur tin zinc sodium mid and far infrared nonlinear optical crystal；In 2090nm
Laser irradiation under, granularity is 0.105-0.15 μm of Na2ZnSn2S6Frequency-doubled effect is commercialized S-Ga-Ag (AgGaS2)
4 times.
A kind of compound sulphur tin zinc sodium of the present invention, the chemical formula of the compound are Na2ZnSn2S6, molecular weight
541.09, it is crystal grain, is non-centrosymmetric structure, is rhombic system, space group Fdd2, cell parameter α=β=γ=90 °, Z=8, unit-cell volume
The preparation method of the compound sulphur tin zinc sodium, follows these steps to carry out:
A, 2:1:2:6 in mass ratio weighs simple substance in the closed container of water content and the equal 0.01-0.1ppm of oxygen content
Sodium, simple substance zinc, simple substance tin and elemental sulfur are uniformly mixed, and are put into clean graphite crucible, are then charged into quartz glass tube, will
Quartz ampoule is 10 in vacuum degree-5-10-3Pa is sealed after vacuumizing；
It b, is to be kept the temperature after 35-40 DEG C/h is warming up to 650-750 DEG C with heating rate by the quartz ampoule sealed in step a, it is former
That reacts between each ingredient in feed composition obtains sulphur tin zinc sodium, and wherein heating-up time and soaking time amount to 100-120h；
C, the sulphur tin zinc sodium in step b is cooled with the rate of 3-5 DEG C/h of temperature, obtains compound sulphur tin zinc sodium
Na2ZnSn2S6。
A kind of sulphur tin zinc sodium mid and far infrared nonlinear optical crystal, the crystal-chemical formula are Na2ZnSn2S6, molecular weight
541.09, it is non-centrosymmetric structure, is rhombic system, space group Fdd2, cell parameter α=β=γ=90 °, Z=8, unit-cell volume
The preparation method of the sulphur tin zinc sodium mid and far infrared nonlinear optical crystal, follows these steps to carry out:
A, 2:1:2:6 in mass ratio weighs simple substance in the closed container of water content and the equal 0.01-0.1ppm of oxygen content
Sodium, simple substance zinc, simple substance tin and elemental sulfur are uniformly mixed, and are put into clean graphite crucible, are then charged into quartz glass tube, will
Quartz ampoule is 10 in vacuum degree-5-10-3Pa is sealed after vacuumizing；
It b, is to be kept the temperature after 35-40 DEG C/h is warming up to 650-750 DEG C with heating rate by the quartz ampoule sealed in step a, it is former
That reacts between each ingredient in feed composition obtains sulphur tin zinc sodium, and wherein heating-up time and soaking time amount to 100-120h；
C, the compound in step b is cooled with the rate of 3-5 DEG C/h of temperature, obtains sulphur tin zinc sodium Na2ZnSn2S6
Mid and far infrared nonlinear optical crystal.
Gas-tight container described in step a is inert gas filled glove box.
The inert gas is nitrogen.
Quartz ampoule is heated to 700 DEG C in step b.
The rate that compound cools in step c is 4 DEG C/h.
The sulphur tin zinc sodium mid and far infrared nonlinear optical crystal is preparing infrared band laser frequency-changer crystal, infrared electricity-
Purposes in electro-optical device, infrared communication device or infrared laser guidance device.
In sulphur tin zinc sodium mid and far infrared nonlinear optical crystal structure of the present invention, Na atom, Sn atom, Zn atom, S
The chemical valence of atom is respectively+1 ,+4 ,+2, -2.Zn atom and neighbouring four S atoms form isolated existing [ZnS4] tetrahedron
Structure；Also adjacent four S atoms form [SnS to Sn atom4] tetrahedron, and chain knot is formed in a manner of total fixed point
Structure.[SnS4] tetrahedroid at chain and [ZnS4] tetrahedroid at layer pinpoint connection altogether, be alternately arranged along a axis.Na atom
It is embedded in [SnS4] tetrahedron and [ZnS4] tetrahedroid at hexagon duct in, formed [NaS5] polygon.All originals
Son is interconnected to form tridimensional network.
Detailed description of the invention
Fig. 1 is the comparison diagram of polycrystal powder X-ray powder diffraction figure and theoretical value of the present invention, and wherein A is experiment value, and B is
Theoretical value.
Fig. 2 is Na of the present invention2ZnSn2S6The structure chart of crystal.
Fig. 3 is sulphur tin zinc sodium of the present invention under 2090nm laser, when granularity is 0.105-0.15 μm and with granularity sulphur
Gallium silver frequency multiplication comparison diagram, wherein A is AgGaS2Secondary frequency multiplication effect figure, B are Na2ZnSn2S6Secondary frequency multiplication effect figure.
Fig. 4 is nonlinear optical crystal frequency-doubled effect schematic diagram of the present invention.
Specific embodiment
The present invention is described in detail by embodiment.But it is not limited only to given embodiment.
Embodiment 1
The preparation of compound sulphur tin zinc sodium:
A, 2:1:2:6 in mass ratio weighs simple substance in the closed container of water content and the equal 0.01-0.1ppm of oxygen content
Sodium, simple substance zinc, simple substance tin and elemental sulfur are uniformly mixed, and are put into clean graphite crucible, are then charged into quartz glass tube, will
Quartz ampoule is 10 in vacuum degree-5-10-3Pa is sealed after vacuumizing；
It b, is that 35-40 DEG C/h is warming up to 750 DEG C, time 10h with heating rate by the quartz ampoule sealed in step a, heat preservation
60h, that is reacted in feedstock composition between each ingredient obtains compound；
C, the compound in step b is cooled with the rate of 3 DEG C/h of temperature, there are orange bulk crystals in crucible, led to
Single-crystal X-ray diffraction analysis is crossed, shows that the compound is sulphur tin zinc sodium, crystal parameter are as follows: cell parameter is α=β=γ=90 °,Z=8, molecule
Amount is 541.09, belongs to rhombic system, space group Fdd2, and structure is as shown in Fig. 2.
Embodiment 2
The preparation of compound sulphur tin zinc sodium:
By Na:Zn:Sn:S elemental mole ratios 2:1:2:6, in water content and the equal 0.1ppm of oxygen content in closed container
It weighs SODIUM METAL, simple substance zinc, simple substance tin and elemental sulfur to be uniformly mixed, is first placed into clean graphite crucible, is then charged into stone
It in English glass tube, seals, is put in high temperature furnace after being vacuumized to quartz ampoule, protected after so that temperature is reached 600-750 DEG C with 10 hours
Temperature 100 hours, then with the near room temperature of rate of 4 DEG C/h of temperature, obtains orange polycrystal powder, mutually carries out to prepared polycrystalline
X-ray powder diffraction, as a result referring to Fig. 1, as seen from the figure, experiment value is mild with theoretical value, and the powder sample illustrated is
Pure phase.
Embodiment 3
The preparation of compound sulphur tin zinc sodium
By Na:Zn:Sn:S elemental mole ratios 2:1:2:6, in weighed in closed container vulcanized sodium, simple substance zinc, simple substance tin and
Elemental sulfur, wherein the water content and oxygen content in affiliated gas-tight container are respectively less than 0.1ppm, vulcanized sodium, simple substance zinc, simple substance tin
With the ratio between the amount of substance of elemental sulfur 1:1:2:5, it is uniformly mixed, is first placed into clean graphite crucible, is then charged into quartz
It in glass tube, seals, is put in high temperature furnace after being vacuumized to quartz ampoule, reached temperature with 10 hours and kept the temperature after 600-750 DEG C
100 hours, then with the near room temperature of the rate of 4 DEG C/h, orange polycrystal powder is obtained, X-ray is mutually carried out to prepared polycrystalline
Powder diffraction, as a result referring to Fig. 1, as seen from the figure, experiment value is mild with theoretical value, and the powder sample illustrated is pure phase.
Embodiment 4
The preparation of sulphur tin zinc sodium mid and far infrared nonlinear optical crystal:
A, it is pressed in the closed container of water content and the glove box filled with inert nitrogen gas of the equal 0.01ppm of oxygen content
Mass ratio 2:1:2:6 weighs SODIUM METAL, simple substance zinc, simple substance tin and elemental sulfur and is uniformly mixed, and is put into clean graphite crucible, so
Be fitted into quartz glass tube afterwards, by quartz ampoule vacuum degree be 10-5-10-3Pa is sealed after vacuumizing；
B, it is that 40 DEG C/h is warming up to 650 DEG C, time 10h with heating rate by the quartz ampoule sealed in step a, keeps the temperature 90h,
That reacts between each ingredient in feedstock composition obtains compound；
C, the compound in step b is cooled with the rate of 3 DEG C/h of temperature, obtains sulphur tin zinc sodium Na2ZnSn2S6In
Far infrared nonlinear optical crystal.
Embodiment 5
The preparation of sulphur tin zinc sodium mid and far infrared nonlinear optical crystal:
A, matter is pressed in the closed container filled with the glove box of inert nitrogen gas in water content and the equal 0.05ppm of oxygen content
Amount weighs SODIUM METAL, simple substance zinc, simple substance tin and elemental sulfur than 2:1:2:6 and is uniformly mixed, and is put into clean graphite crucible, then
Be fitted into quartz glass tube, by quartz ampoule vacuum degree be 10-5-10-3Pa is sealed after vacuumizing；
It b, is that 35 DEG C/h is warming up to 700 DEG C, time 20h with heating rate by the quartz ampoule sealed in step a, heat preservation
100h, that is reacted in feedstock composition between each ingredient obtains compound；
C, the compound in step b is cooled with the rate of 4 DEG C/h of temperature, obtains sulphur tin zinc sodium Na2ZnSn2S6In
Far infrared nonlinear optical crystal.
Embodiment 6
The preparation of sulphur tin zinc sodium mid and far infrared nonlinear optical crystal:
A, matter is pressed in the closed container filled with the glove box of inert nitrogen gas in water content and the equal 0.1ppm of oxygen content
Amount weighs SODIUM METAL, simple substance zinc, simple substance tin and elemental sulfur than 2:1:2:6 and is uniformly mixed, and is put into clean graphite crucible, then
Be fitted into quartz glass tube, by quartz ampoule vacuum degree be 10-5-10-3Pa is sealed after vacuumizing；
It b, is that 38 DEG C/h is warming up to 750 DEG C, time 10h with heating rate by the quartz ampoule sealed in step a, heat preservation
100h, that is reacted in feedstock composition between each ingredient obtains compound；
C, the compound in step b is cooled with the rate of 5 DEG C/h of temperature, obtains sulphur tin zinc sodium Na2ZnSn2S6In
Far infrared nonlinear optical crystal.
Embodiment 7
By any one sulphur germanium zinc sodium mid and far infrared nonlinear optical crystal obtained in embodiment 4-6, by shown in attached drawing 4
It is placed on 3 position, at room temperature, with adjusting the 2090nm output of Q Ho:Tm:Cr:YAG laser to make light source, observes bright
Aobvious 1045nm frequency multiplication light output, output intensity is equal with equal conditions AgGaS2's, and Fig. 3 is shown, by adjusting Q Ho:Tm:Cr:
YAG laser 1 issues the infrared beam that wavelength is 2090nm and injects sulphur germanium zinc sodium nonlinear optical crystal through convex lens 2, produces
The frequency doubled light that raw wavelength is 1045nm, light of the outgoing beam 4 containing infrared light and 1045nm that wavelength is 2090nm, through filter plate
The frequency doubled light that wavelength is 1045nm is obtained after 5 eliminations.
Claims (7)
1. a kind of sulphur tin zinc sodium mid and far infrared nonlinear optical crystal, it is characterised in that the crystal-chemical formula is Na2ZnSn2S6, point
Son amount 541.09 is non-centrosymmetric structure, is rhombic system, space group Fdd2, cell parameter a=12.945(3), b=
23.556(5), c=7.2774(15), α=β=γ=90 °, Z=8, unit-cell volume V=2219.1(8) 3。
2. the preparation method of sulphur tin zinc sodium mid and far infrared nonlinear optical crystal as described in claim 1, characteristic is, presses
The following steps carry out:
A, 2:1:2:6 in mass ratio weighs SODIUM METAL, list in the closed container of water content and the equal 0.01-0.1ppm of oxygen content
Matter zinc, simple substance tin and elemental sulfur are uniformly mixed, and are put into clean graphite crucible, are then charged into quartz glass tube, will be quartzy
Pipe is 10 in vacuum degree-5-10-3Pa is sealed after vacuumizing；
It b, is to be kept the temperature after 35-40 DEG C/h is warming up to 650-750 DEG C with heating rate by the quartz ampoule sealed in step a, raw material group
It closes to react between each ingredient in object and obtains sulphur tin zinc sodium, wherein heating-up time and soaking time amount to 100-120h；
C, the compound in step b is cooled with the rate of 3-5 DEG C/h of temperature, obtains sulphur tin zinc sodium Na2ZnSn2S6In it is remote
Infrared nonlinear optical crystal.
3. the preparation method of sulphur tin zinc sodium mid and far infrared nonlinear optical crystal as claimed in claim 2, it is characterised in that step
Closed container described in rapid a is inert gas filled glove box.
4. the preparation method of sulphur tin zinc sodium mid and far infrared nonlinear optical crystal as claimed in claim 3, it is characterised in that institute
Stating inert gas is nitrogen.
5. the preparation method of sulphur tin zinc sodium mid and far infrared nonlinear optical crystal as claimed in claim 2, it is characterised in that step
Quartz ampoule is heated to 700 DEG C in rapid b.
6. the preparation method of sulphur tin zinc sodium mid and far infrared nonlinear optical crystal as claimed in claim 2, it is characterised in that step
The rate that compound cools in rapid c is 4 DEG C/h.
7. sulphur tin zinc sodium mid and far infrared nonlinear optical crystal as described in claim 1 is preparing infrared band laser frequency conversion crystalline substance
Purposes in body, infrared electro-optical device, infrared communication device or infrared laser guidance device.
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| CN108588840B (en) * | 2018-06-15 | 2020-12-11 | 中国科学院新疆理化技术研究所 | Barium borosulfide middle and far infrared nonlinear optical crystal and preparation method and application thereof |
| CN110607556A (en) * | 2019-09-23 | 2019-12-24 | 中国科学院福建物质结构研究所 | Crystal material, preparation and growth method thereof and application of crystal material in nonlinear optics |
| CN112981536A (en) * | 2021-02-10 | 2021-06-18 | 天津理工大学 | Compound barium zinc tin sulfur oxide and barium zinc tin sulfur oxide nonlinear optical crystal, preparation method and application |
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| CN102976287A (en) * | 2011-09-02 | 2013-03-20 | 中国科学院理化技术研究所 | BaGa2GeSe6 compound, BaGa2GeSe6 non-linear optical crystal and their preparation methods and use |
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| CN105803531A (en) * | 2016-04-13 | 2016-07-27 | 浙江大学 | Four-element selenide non-linear optical crystal and preparing method and application thereof |
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| CN102838093A (en) * | 2011-06-21 | 2012-12-26 | 中国科学院理化技术研究所 | LiGaGe2Se6 compound, LiGaGe2Se6 nonlinear optical crystals, and preparation method and application thereof |
| CN102976287A (en) * | 2011-09-02 | 2013-03-20 | 中国科学院理化技术研究所 | BaGa2GeSe6 compound, BaGa2GeSe6 non-linear optical crystal and their preparation methods and use |
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Non-Patent Citations (1)
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| Na2ZnGe2S6: A New Infrared Nonlinear Optical Material with Good Balance between Large Second-Harmonic Generation Response and High Laser Damage Threshold;Guangmao Li et al.;《J. Am. Chem. Soc.》;20160519;第138卷;第7422-7428页 * |
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