CN107557867A - 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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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, it is crystal grain.The chemical formula of the crystal is Na2ZnSn2S6, molecular weight 541.09, it is non-centrosymmetric structure, is rhombic system, space group Fdd2, 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）Å3；Using by SODIUM METAL, simple substance zinc, the solid phase reaction of simple substance tin and elemental sulfur under vacuum；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 2090nm laser irradiation, 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 field, 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 technology
Non-linear optical crystal material, three major types can be classified as according to its scope through wave band：First, it is ultraviolet and dark purple
Wave section nonlinear optical material；2nd, visible ray and near infrared band nonlinear optical material；3rd, infrared and mid and far infrared is non-
Linear optical material.The work of the present invention belongs to visible ray 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 communicationses, 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.Infrared nonlinear optical crystal in the market, common infrared non-linear optics are brilliant
Body mainly has AgGaS2, AgGaSe2, ZnGeP2Deng.Although these crystal are all in civilian production life high-tech area and military affairs
Acted in equipment, but the shortcomings that these crystalline materials also have itself, and people's reason is also unable to reach in combination property
The requirement thought, with development and the desired raising of technology, the demand of the infrared non-linear crystal more excellent to performance is more
It is urgent, therefore for the exploration of new mid and far infrared nonlinear crystal, in terms of civilian high-tech industry and lifting military equipment
All there is important strategic importance, and crystalline material synthesis and growth are a kind of huge challenges of the direction.
The content of the invention
It is an object of the present invention to provide a kind of sulphur tin zinc sodium and sulphur tin zinc sodium mid and far infrared nonlinear optical crystal and system
Preparation Method and application, the chemical formula of the compound is Na2ZnSn2S6, molecular weight 541.09, it is polycrystal powder.The chemistry of the crystal
Formula is Na2ZnSn2S6, molecular weight 541.09, it is non-centrosymmetric structure, is rhombic system, space group Fdd2, cell parameter
Forα=β=γ=90 °, Z=8, unit-cell volumeUsing by SODIUM METAL, simple substance zinc, the solid phase reaction of simple substance tin and elemental sulfur under vacuum；This hair
The powder xrd pattern and theoretical calculation of bright sulphur tin zinc sodium and sulphur tin zinc sodium mid and far infrared nonlinear optical crystal；2090nm's
Under laser irradiation, 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 is Na2ZnSn2S6, molecular weight 541.09,
It is non-centrosymmetric structure for crystal grain, 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, in mass ratio 2 in water content and the equal 0.01-0.1ppm of oxygen content closed container:1:2:6 weigh simple substance
Sodium, simple substance zinc, simple substance tin and elemental sulfur are well mixed, and are put into clean graphite crucible, are then charged into quartz glass tube, will
Quartz ampoule is 10 in vacuum-5-10-3Pa is sealed after vacuumizing；
B, it is incubated after the quartz ampoule sealed in step a being warming up into 650-750 DEG C as 35-40 DEG C/h using heating rate, it is former
That is reacted in feed composition between each composition obtains sulphur tin zinc sodium, and the wherein heating-up time amounts to 100-120h with soaking time；
C, the sulphur tin zinc sodium in step b is cooled with 3-5 DEG C/h of temperature speed, 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 rhombic system for non-centrosymmetric structure, 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, in mass ratio 2 in water content and the equal 0.01-0.1ppm of oxygen content closed container:1:2:6 weigh simple substance
Sodium, simple substance zinc, simple substance tin and elemental sulfur are well mixed, and are put into clean graphite crucible, are then charged into quartz glass tube, will
Quartz ampoule is 10 in vacuum-5-10-3Pa is sealed after vacuumizing；
B, it is incubated after the quartz ampoule sealed in step a being warming up into 650-750 DEG C as 35-40 DEG C/h using heating rate, it is former
That is reacted in feed composition between each composition obtains sulphur tin zinc sodium, and the wherein heating-up time amounts to 100-120h with soaking time；
C, the compound in step b is cooled with 3-5 DEG C/h of temperature speed, 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 speed that compound cools in step c is 4 DEG C/h.
The sulphur tin zinc sodium mid and far infrared nonlinear optical crystal prepare infrared band laser frequency-changer crystal, it is 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 atoms, Sn atoms, Zn atoms, S
The chemical valence of atom is respectively+1 ,+4 ,+2, -2.Zn atoms form isolated existing [ZnS with neighbouring four S atoms4] tetrahedron
Structure；Also adjacent four S atoms form [SnS to Sn atoms4] tetrahedron, and chain knot is formed in a manner of common fixed point
Structure.[SnS4] tetrahedroid into chain and [ZnS4] tetrahedroid into layer pinpoint connection altogether, be alternately arranged along a axles.Na atoms
It is embedded in [SnS4] tetrahedron and [ZnS4] tetrahedroid into hexagon duct in, formed [NaS5] polygon.All originals
Son, it is interconnected to form tridimensional network.
Brief description of the drawings
Fig. 1 is the comparison diagram of polycrystal powder X-ray powder diffraction figure of the present invention and theoretical value, 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 be sulphur tin zinc sodium of the present invention under 2090nm laser, granularity be 0.105-0.15 μm when 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.
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, in mass ratio 2 in water content and the equal 0.01-0.1ppm of oxygen content closed container:1:2:6 weigh simple substance
Sodium, simple substance zinc, simple substance tin and elemental sulfur are well mixed, and are put into clean graphite crucible, are then charged into quartz glass tube, will
Quartz ampoule is 10 in vacuum-5-10-3Pa is sealed after vacuumizing；
B, the quartz ampoule sealed in step a is warming up to 750 DEG C, time 10h by 35-40 DEG C/h of heating rate, insulation
60h, that is reacted between each composition in feedstock composition obtains compound；
C, the compound in step b is cooled with 3 DEG C/h of temperature speed, there are orange bulk crystals in crucible, led to
Single-crystal X-ray diffraction analysis is crossed, it is sulphur tin zinc sodium to show the compound, and crystal parameter is：Cell parameter is α=β=γ=90 °,Z=8, its molecule
Measure as 541.09, belong to rhombic system, space group Fdd2, structure is as shown in Figure 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
Weigh SODIUM METAL, simple substance zinc, simple substance tin and elemental sulfur to be well mixed, be first placed into clean graphite crucible, be then charged into stone
In English glass tube, seal, be put in high temperature furnace after being vacuumized to quartz ampoule, temperature is protected after reaching 600-750 DEG C with 10 hours
Temperature 100 hours, then with 4 DEG C/h of the temperature near room temperature of speed, obtains orange polycrystal powder, and prepared more crystalline phases are carried out
X-ray powder diffraction, as a result referring to Fig. 1, as seen from the figure, experiment value is gentle with theoretical value, and the powder sample for illustrating to obtain 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 material of elemental sulfur 1:1:2:5, it is well mixed, is first placed into clean graphite crucible, is then charged into quartz
In glass tube, seal, be put in high temperature furnace after being vacuumized to quartz ampoule, reached temperature with 10 hours and be incubated after 600-750 DEG C
100 hours, then with the near room temperature of 4 DEG C/h speed, orange polycrystal powder is obtained, X ray is carried out to prepared more crystalline phases
Powder diffraction, as a result referring to Fig. 1, as seen from the figure, experiment value is gentle with theoretical value, and the powder sample for illustrating to obtain is pure phase.
Embodiment 4
The preparation of sulphur tin zinc sodium mid and far infrared nonlinear optical crystal：
A, pressed in the closed container of water content and the equal 0.01ppm of the oxygen content glove box filled with inert nitrogen gas
Mass ratio 2:1:2:6, which weigh SODIUM METAL, simple substance zinc, simple substance tin and elemental sulfur, is well mixed, and is put into clean graphite crucible, so
Be fitted into afterwards in quartz glass tube, by quartz ampoule vacuum be 10-5-10-3Pa is sealed after vacuumizing；
B, the quartz ampoule sealed in step a is warming up to 650 DEG C, time 10h by 40 DEG C/h of heating rate, is incubated 90h,
That is reacted in feedstock composition between each composition obtains compound；
C, the compound in step b is cooled with 3 DEG C/h of temperature speed, 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 of the glove box filled with inert nitrogen gas in water content and the equal 0.05ppm of oxygen content
Measure ratio 2:1:2:6, which weigh SODIUM METAL, simple substance zinc, simple substance tin and elemental sulfur, is well mixed, and is put into clean graphite crucible, then
Be fitted into quartz glass tube, by quartz ampoule vacuum be 10-5-10-3Pa is sealed after vacuumizing；
B, the quartz ampoule sealed in step a is warming up to 700 DEG C, time 20h by 35 DEG C/h of heating rate, insulation
100h, that is reacted between each composition in feedstock composition obtains compound；
C, the compound in step b is cooled with 4 DEG C/h of temperature speed, 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 of the glove box filled with inert nitrogen gas in water content and the equal 0.1ppm of oxygen content
Measure ratio 2:1:2:6, which weigh SODIUM METAL, simple substance zinc, simple substance tin and elemental sulfur, is well mixed, and is put into clean graphite crucible, then
Be fitted into quartz glass tube, by quartz ampoule vacuum be 10-5-10-3Pa is sealed after vacuumizing；
B, the quartz ampoule sealed in step a is warming up to 750 DEG C, time 10h by 38 DEG C/h of heating rate, insulation
100h, that is reacted between each composition in feedstock composition obtains compound；
C, the compound in step b is cooled with 5 DEG C/h of temperature speed, obtains sulphur tin zinc sodium Na2ZnSn2S6In
Far infrared nonlinear optical crystal.
Embodiment 7
By in embodiment 4-6 gained any one sulphur germanium zinc sodium mid and far infrared nonlinear optical crystal, as shown in accompanying drawing 4
It is placed on 3 position, at room temperature, with tune Q Ho:Tm:Cr:Light source is made in the 2090nm outputs of YAG laser, it was observed that bright
Aobvious 1045nm frequency multiplication light outputs, output intensity is equal with equal conditions AgGaS2's, and Fig. 3 is shown, by adjusting Q Ho:Tm:Cr:
YAG laser 1 sends the infrared beam that wavelength is 2090nm and injects sulphur germanium zinc sodium nonlinear optical crystal, production through convex lens 2
Raw wavelength is 1045nm frequency doubled light, and outgoing beam 4 is containing the infrared light that wavelength is 2090nm and 1045nm light, filtered
The frequency doubled light that wavelength is 1045nm is obtained after 5 eliminations.
Claims (9)
1. a kind of compound sulphur tin zinc sodium, it is characterised in that the chemical formula of the compound is Na2ZnSn2S6, molecular weight 541.09,
It is non-centrosymmetric structure for crystal grain, 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）Å 3。
2. the preparation method of compound sulphur tin zinc sodium according to claim 1, it is characterised in that follow these steps to carry out：
A, in mass ratio 2 in water content and the equal 0.01-0.1ppm of oxygen content closed container:1:2:6 weigh SODIUM METAL, list
Matter zinc, simple substance tin and elemental sulfur are well mixed, and are put into clean graphite crucible, are then charged into quartz glass tube, by quartz
Pipe is 10 in vacuum-5-10-3Pa is sealed after vacuumizing；
B, it is incubated after the quartz ampoule sealed in step a being warming up into 650-750 DEG C as 35-40 DEG C/h using heating rate, raw material group
That is reacted in compound between each composition obtains sulphur tin zinc sodium, and the wherein heating-up time amounts to 100-120h with soaking time；
C, the sulphur tin zinc sodium in step b is cooled with 3-5 DEG C/h of temperature speed, obtains compound sulphur tin zinc sodium
Na2ZnSn2S6。
3. 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）Å 3。
4. the preparation method of sulphur tin zinc sodium mid and far infrared nonlinear optical crystal as claimed in claim 1, its characteristic is, presses
The following steps are carried out：
A, in mass ratio 2 in water content and the equal 0.01-0.1ppm of oxygen content closed container:1:2:6 weigh SODIUM METAL, list
Matter zinc, simple substance tin and elemental sulfur are well mixed, and are put into clean graphite crucible, are then charged into quartz glass tube, by quartz
Pipe is 10 in vacuum-5-10-3Pa is sealed after vacuumizing；
B, it is incubated after the quartz ampoule sealed in step a being warming up into 650-750 DEG C as 35-40 DEG C/h using heating rate, raw material group
That is reacted in compound between each composition obtains sulphur tin zinc sodium, and the wherein heating-up time amounts to 100-120h with soaking time；
C, the compound in step b is cooled with 3-5 DEG C/h of temperature speed, obtains sulphur tin zinc sodium Na2ZnSn2S6In it is remote
Infrared nonlinear optical crystal.
5. the preparation method of sulphur tin zinc sodium mid and far infrared non-linear optical crystal as claimed in claim 4, it is characterised in that step a
Described in gas-tight container be inert gas filled glove box.
6. the preparation method of sulphur tin zinc sodium mid and far infrared nonlinear optical crystal as claimed in claim 5, it is characterised in that institute
It is nitrogen to state inert gas.
7. the preparation method of sulphur tin zinc sodium mid and far infrared nonlinear optical crystal as claimed in claim 4, it is characterised in that step
Quartz ampoule is heated to 700 DEG C in rapid b.
8. the preparation method of sulphur tin zinc sodium mid and far infrared nonlinear optical crystal as claimed in claim 4, it is characterised in that step
The speed that compound cools in rapid c is 4 DEG C/h.
9. sulphur tin zinc sodium mid and far infrared nonlinear optical crystal as claimed in claim 3 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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Cited By (3)
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| CN108588840A (en) * | 2018-06-15 | 2018-09-28 | 中国科学院新疆理化技术研究所 | Boron barium sulphide mid and far infrared nonlinear optical crystal and preparation method and application |
| 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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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108588840A (en) * | 2018-06-15 | 2018-09-28 | 中国科学院新疆理化技术研究所 | Boron barium sulphide mid and far infrared nonlinear optical crystal and preparation method and application |
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| 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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