CN103484939B - Infrared nonlinear optical crystal Ba3BSbS6And its production and use - Google Patents
Infrared nonlinear optical crystal Ba3BSbS6And its production and use Download PDFInfo
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- CN103484939B CN103484939B CN201310469418.2A CN201310469418A CN103484939B CN 103484939 B CN103484939 B CN 103484939B CN 201310469418 A CN201310469418 A CN 201310469418A CN 103484939 B CN103484939 B CN 103484939B
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Abstract
The present invention relates to infrared nonlinear optical crystal Ba3BSbS6And preparation method thereof, belong to Inorganic Nonlinear Optical Materials field.Synthesized using high temperature solid-state method, synthesis infrared nonlinear optical crystal Ba3BSbS6, belong to hexagonal crystal system, space group isCompound Ba3BSbS6Under 2.05 μm of laser excitation, its powder frequency doubling intensity is AgGaS23 times.
Description
Technical field
The present invention relates to non-centrosymmetrical thioborate compound-material of a kind of crystallography and preparation method thereof, belong to
Inorganic Nonlinear Optical Materials field.
Background technology
Infrared nonlinear optical crystal laser technology, military affairs and it is civilian on played more and more important effect.But
Existing commercial material, such as ZnGeP2, AgGaS2, LiGaS2, LiInS2Etc. the defects such as laser damage threshold is low being present, it is impossible to full
The growing practical application request of foot.Therefore exploration discovery can be provided simultaneously with high laser damage threshold and greatly non-linear
The new and effective infrared nonlinear optical crystal material of optical coefficient is a difficult point and focus in the field.In numerous chalcogens
In compound, thioborate is due to its abundant anionic group（Such as [BS3]3-Planar delta, [BS4]5-Tetrahedron, [B3S6
]3-Hexatomic ring, [B4S10]8-Huge tetrahedron, [B10S16S4/2]6-Super tetrahedron and other bigger anionic groups）Cause me
The interest studied.If asymmetric cell mentioned above can form non-core structure, especially [BS3]3-Planar delta or
[BS4]5-If tetrahedron energy same-phase arrangement produces the compound of non-core structure, then their existing strong dipoles are with polarization with regard to energy
Enough inductions produce strong SHG responses.In addition, research shows that thioborate is that one kind can integrate the wide transmission scope of sulfide
It is and high non-linear（Such as AgGaS2）And borate（Such as LiB3O5With β-BaB2O4）One kind of high laser damage threshold
Compound.At present, quantity is mostly that ternary phase contains alkali or alkaline earth metal compound than relatively limited thioborate, and most of is
Centrosymmetric structure.The thioborate with nonlinear optical response reported only has one, i.e. S.W.Martin et al.
The quaternary compound Zn of synthesisxBa2B2S5+x(x ≈ 0.2), its shg efficiency are about α-SiO250 times.The present invention is by appropriate
Introduce second of asymmetric cell [SbS3]3-In Ba/B/S systems, the noval chemical compound of a non-core structure is successfully obtained
Ba3BSbS6.Powder nonlinear optical property measurement shows, Ba3BSbS6Compound has excellent nonlinear optical property, this
Impart the excellent infrared non-linear optical property of the compounds.Related work, document report that so far there are no.
The content of the invention
The purpose of the present invention：(1) an infrared nonlinear optical crystal is provided, its chemical formula is Ba3BSbS6；(2) provide
Nonlinear optical crystal Ba3BSbS6Preparation method；(3) nonlinear optical crystal Ba is provided3BSbS6Purposes.
The invention provides nonlinear optical crystal Ba3BSbS6Monocrystal.The monocrystal, belong to hexagonal crystal system, space
Group beWherein, Ba3BSbS6Cell parameter be α=β
=90 °, γ=120 °, Z=3, unit cell volume isThe compound crystal structure is as shown in figure 1, structure master
It is characterized as isolated dissymmetrical structure unit [BS3]3-Planar delta and [SbS3]3-Pyrometric cone, Ba2+Around being distributed in.
The invention provides nonlinear optical crystal Ba3BSbS6Preparation method, comprise the following steps：By Ba, B, Sb, S
By 3:1:1:6 ratio is well mixed, using high temperature solid phase synthesis, in 820 DEG C of sintering, constant temperature after 100 hours on an hourly basis
5 DEG C of speed is cooled to 300 DEG C, closes stove；After sample is cooled to room temperature, you can obtain nonlinear optical crystal
Ba3BSbS6, XRD detections are carried out to its sample powder, as a result such as Fig. 2.
The invention provides nonlinear optical crystal Ba3BSbS6Purposes, it is characterised in that：The nonlinear optical crystal is used
In the frequency transformation of laser device laser output.Powder frequency doubling, which is tested, to be shown, compound Ba3BSbS6With excellent nonlinear optics
Property, under 2.05 μm of laser excitation, its powder frequency doubling intensity is AgGaS2(AGS) 3 times, related data is shown in Fig. 3.It is expected that
There is significant application value in high-tech areas such as laser frequency conversion, Electro-optical Modulation, Preset grating information processings.
Brief description of the drawings
Fig. 1 is Ba3BSbS6Crystal structure schematic diagram.
Fig. 2 is Ba3BSbS6Crystal X-Ray Diffraction collection of illustrative plates.Wherein, a, b are respectively Ba3(BS3)(SbS3) crystal experiment and
Theoretical X ray diffracting spectrum.
Fig. 3 is Ba3BSbS6Crystal powder frequency multiplication intensity reference and AgGaS2Graph of a relation (the incident laser ripple of (46-74 μm)
A length of 2050nm).
Embodiment
Ba, B, Sb, S are pressed 3 in glove box:1:1:6 ratio is well mixed, and is placed in crystal reaction tube, in Gao Zhen
Flame seals under reciprocal of duty cycle.The crystal reaction tube sealed is placed in the tube furnace of temperature programmed control, and 820 are warming up to by 35h
DEG C, 100h is incubated, then 300 DEG C is down to by 104h, cuts off furnace power afterwards, target is can obtain after being down to room temperature naturally
Crystal（X-ray monocrystalline is tested）And powder pure phase.
Claims (3)
1. infrared nonlinear optical crystal Ba3BSbS6, it is characterised in that：Its molecular formula is Ba3BSbS6, belong to hexagonal crystal system, it is empty
Between group beCell parameter isα=β=90 °, γ=
120 °, Z=3, unit cell volume is
2. the preparation method of the infrared nonlinear optical crystal described in claim 1, using one-step synthesis, including following step
Suddenly：By Ba, B, Sb, S Ba in proportion:B:Sb:S=3:1:1:After 6 is well mixed, using high temperature solid phase synthesis, in 820 DEG C of burnings
Knot, is cooled to room temperature, you can obtains compound Ba3BSbS6。
3. the nonlinear optical crystal described in claim 1 is used for the frequency transformation of laser device laser output.
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| CN103484939B true CN103484939B (en) | 2018-02-16 |
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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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