CN103484939A - Infrared nonlinear optical crystal Ba3BSbS6, and preparation method and purpose thereof - Google Patents
Infrared nonlinear optical crystal Ba3BSbS6, and preparation method and purpose thereof Download PDFInfo
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- CN103484939A CN103484939A CN201310469418.2A CN201310469418A CN103484939A CN 103484939 A CN103484939 A CN 103484939A CN 201310469418 A CN201310469418 A CN 201310469418A CN 103484939 A CN103484939 A CN 103484939A
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- nonlinear optical
- ba3bsbs6
- bsbs
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Abstract
The present invention relates to infrared nonlinear optical crystal Ba3BSbS6 and preparation method thereof, belong to Inorganic Nonlinear Optical Materials field. It is synthesized using high temperature solid-state method, synthesizes infrared nonlinear optical crystal Ba3BSbS6, belong to hexagonal crystal system, space group is
For compound Ba3BSbS6 under 2.05 μm of laser excitation, powder frequency doubling intensity is 3 times of AgGaS2.
Description
Technical field
The present invention relates to a crystalloid and learn non-centrosymmetrical thioborate compound-material and preparation method thereof, belong to the Inorganic Nonlinear Optical Materials field.
Background technology
Infrared nonlinear optical crystal laser technology, military affairs and civilian on brought into play more and more important effect.Yet existing commercial material, as ZnGeP
2, AgGaS
2, LiGaS
2, LiInS
2deng there being the defects such as laser damage threshold is low, can not meet growing practical application request.Therefore exploration discovery can possess difficult point and the focus that the new and effective infrared nonlinear optical crystal material of high laser damage threshold and large nonlinear optical coefficients is these fields simultaneously.In numerous chalcogen compounds, thioborate due to its abundant anionic group (as [BS
3]
3-planar delta, [BS
4]
5-tetrahedron, [B
3s
6]
3-six-ring, [B
4s
10]
8-huge tetrahedron, [B
10s
16s
4/2]
6-super tetrahedron and other larger anionic group) caused the interest of our research.If the asymmetric cell of mentioning above-mentioned can form non-core structure, especially [BS
3]
3-planar delta or [BS
4]
5-if tetrahedron can same-phase be arranged the compound that produces non-core structure, the strong dipole that they exist so and polarization just can be induced and be produced strong SHG response.In addition, research show thioborate be a class comprehensively sulfide wide for example, through scope and high non-linear (AgGaS
2) and borate (LiB for example
3o
5and β-BaB
2o
4) compounds of high laser damage threshold.At present, the more limited thioborate of quantity mostly is ternary phase containing alkali or alkaline earth metal compound, and symmetrical structure centered by great majority.The thioborate with nonlinear optical response of having reported only has an example, i.e. the synthetic quaternary compound Zn of people such as S.W.Martin
xba
2b
2s
5+x(x ≈ 0.2), its shg efficiency is about α-SiO
250 times.The present invention is by appropriate the second asymmetric cell [SbS that introduces
3]
3-in the Ba/B/S system, the new compound Ba that obtains a routine non-core structure of success
3bSbS
6.The measurement of powder nonlinear optical property shows, Ba
3bSbS
6compound has good nonlinear optical property, and this has given this compounds good infrared non-linear optical property.Related work, so far there are no bibliographical information.
Summary of the invention
Purpose of the present invention: (1) provides a routine infrared nonlinear optical crystal, and its chemical formula is Ba
3bSbS
6; (2) provide non-linear optic crystal Ba
3bSbS
6the preparation method; (3) provide non-linear optic crystal Ba
3bSbS
6purposes.
The invention provides non-linear optic crystal Ba
3bSbS
6single crystal.This single crystal, belong to hexagonal system, and spacer is
wherein, Ba
3bSbS
6unit cell parameters be
α=β=90 °, γ=120 °, Z=3, unit cell volume is
as shown in Figure 1, the structure principal character is isolated unsymmetrical structure unit [BS to this compound crystal structure
3]
3-planar delta and [SbS
3]
3-pyrometric cone, Ba
2+around being distributed in.
The invention provides non-linear optic crystal Ba
3bSbS
6the preparation method, comprise the steps: Ba, B, Sb, S are mixed in the ratio of 3:1:1:6, adopt high temperature solid phase synthesis, at 820 ℃ of sintering, constant temperature was cooled to 300 ℃ by the speed of 5 ℃ per hour after 100 hours, closed stove; After sample is cooled to room temperature, can obtain non-linear optic crystal Ba
3bSbS
6, its sample powder is carried out to the XRD detection, result is as Fig. 2.
The invention provides non-linear optic crystal Ba
3bSbS
6purposes, it is characterized in that: this non-linear optic crystal is for the frequency transformation of laser device laser output.The powder frequency doubling test shows, compd B a
3bSbS
6have good nonlinear optical property, under 2.05 μ m laser excitations, its powder frequency doubling intensity is AgGaS
2(AGS) 3 times, related data is shown in Fig. 3.Be expected at laser frequency conversion, Electro-optical Modulation, light is sold off the high-tech areas such as information processing that significant application value is arranged.
The accompanying drawing explanation
Fig. 1 is Ba
3bSbS
6the crystalline structure schematic diagram.
Fig. 2 is Ba
3bSbS
6the Crystal X-Ray Diffraction collection of illustrative plates.Wherein, a, b is respectively Ba
3(BS
3) (SbS
3) experiment and the theoretical X ray diffracting spectrum of crystal.
Fig. 3 is Ba
3bSbS
6crystal powder frequency multiplication intensity reference and AgGaS
2the graph of a relation (laser wavelength of incidence is 2050nm) of (46 – 74 μ m).
Embodiment
In glove box, Ba, B, Sb, S are mixed in the ratio of 3:1:1:6, be placed in crystal reaction tube, flame sealing by fusing under condition of high vacuum degree.The crystal reaction tube of sealing is placed in the tube furnace of temperature programmed control, be warming up to 820 ℃ through 35h, insulation 100h, then be down to 300 ℃ through 104h, cut off afterwards the stove power supply, can obtain target crystal (test of X-ray monocrystalline) and powder pure phase after naturally being down to room temperature.
Claims (3)
1. infrared nonlinear optical crystal Ba
3bSbS
6, it is characterized in that: its molecular formula is Ba
3bSbS
6, belonging to hexagonal system, spacer is
unit cell parameters is
α=β=90 °, γ=120 °, Z=3, unit cell volume is
2. the preparation method of infrared nonlinear optical crystal claimed in claim 1, adopt one-step synthesis, after comprising the steps: Ba, B, Sb, S are mixed by suitable proportion, adopt high temperature solid phase synthesis, at 820 ℃ of sintering, be cooled to room temperature, can obtain compd B a
3bSbS
6.
3. non-linear optic crystal claimed in claim 1 is for the frequency transformation of laser device laser output.
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|---|---|---|---|
| CN201310469418.2A CN103484939B (en) | 2013-10-10 | 2013-10-10 | Infrared nonlinear optical crystal Ba3BSbS6And its production and use |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310469418.2A CN103484939B (en) | 2013-10-10 | 2013-10-10 | Infrared nonlinear optical crystal Ba3BSbS6And its production and use |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN103484939A true CN103484939A (en) | 2014-01-01 |
| CN103484939B CN103484939B (en) | 2018-02-16 |
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ID=49825515
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6508960B1 (en) * | 1999-07-26 | 2003-01-21 | The United States Of America As Represented By The Secretary Of The Air Force | Telluride quaternary nonlinear optic materials |
| CN101024899A (en) * | 2006-02-21 | 2007-08-29 | 中国科学院福建物质结构研究所 | Non-linear optical crystal selenium borate |
| CN102230225A (en) * | 2011-06-27 | 2011-11-02 | 中国科学院福建物质结构研究所 | Nonlinear optical crystal gallium germanium barium selenide as well as growing method and purposes thereof |
| CN102534784A (en) * | 2010-12-16 | 2012-07-04 | 中国科学院福建物质结构研究所 | Nonlinear optical crystal Rb4Ge3B6O17 |
| CN103031607A (en) * | 2012-12-12 | 2013-04-10 | 中国科学院福建物质结构研究所 | Infrared nonlinear optical crystal AB4C5Se12 |
-
2013
- 2013-10-10 CN CN201310469418.2A patent/CN103484939B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6508960B1 (en) * | 1999-07-26 | 2003-01-21 | The United States Of America As Represented By The Secretary Of The Air Force | Telluride quaternary nonlinear optic materials |
| CN101024899A (en) * | 2006-02-21 | 2007-08-29 | 中国科学院福建物质结构研究所 | Non-linear optical crystal selenium borate |
| CN102534784A (en) * | 2010-12-16 | 2012-07-04 | 中国科学院福建物质结构研究所 | Nonlinear optical crystal Rb4Ge3B6O17 |
| CN102230225A (en) * | 2011-06-27 | 2011-11-02 | 中国科学院福建物质结构研究所 | Nonlinear optical crystal gallium germanium barium selenide as well as growing method and purposes thereof |
| CN103031607A (en) * | 2012-12-12 | 2013-04-10 | 中国科学院福建物质结构研究所 | Infrared nonlinear optical crystal AB4C5Se12 |
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