CN109137081A - A kind of Hg2GeSe4The preparation method and applications of nonlinear optical crystal - Google Patents
A kind of Hg2GeSe4The preparation method and applications of nonlinear optical crystal Download PDFInfo
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- CN109137081A CN109137081A CN201810297506.1A CN201810297506A CN109137081A CN 109137081 A CN109137081 A CN 109137081A CN 201810297506 A CN201810297506 A CN 201810297506A CN 109137081 A CN109137081 A CN 109137081A
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- gese
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- optical crystal
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- C—CHEMISTRY; METALLURGY
- C30—CRYSTAL GROWTH
- C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
- C30B29/00—Single crystals or homogeneous polycrystalline material with defined structure characterised by the material or by their shape
- C30B29/10—Inorganic compounds or compositions
- C30B29/46—Sulfur-, selenium- or tellurium-containing compounds
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- C—CHEMISTRY; METALLURGY
- C30—CRYSTAL GROWTH
- C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
- C30B11/00—Single-crystal growth by normal freezing or freezing under temperature gradient, e.g. Bridgman-Stockbarger method
-
- G—PHYSICS
- G02—OPTICS
- G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
- G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
- G02F1/35—Non-linear optics
- G02F1/355—Non-linear optics characterised by the materials used
- G02F1/3551—Crystals
Abstract
The invention discloses a kind of Hg2GeSe4The preparation method and applications of nonlinear optical crystal, the Hg2GeSe4Nonlinear optical crystal does not have symmetrical centre, belongs to tetragonal crystal system, space group I4 ‑, cell parameter are as follows:α=β=γ=90 °, Z=2.The invention also discloses the nonlinear optical crystal is prepared using high-temperature fusant spontaneous crystallization method and Bridgman-Stockbarger method.The Hg that the present invention prepares2GeSe4Nonlinear optical crystal can be used for making device for non-linear optical.
Description
Technical field
The invention belongs to the preparation fields of nonlinear optical crystal, in particular it relates to a kind of Hg2GeSe4It is non-thread
Property optical crystal (Hg2GeSe4Monocrystalline) and the Hg2GeSe4The preparation method and application of monocrystalline and contain the Hg2GeSe4Monocrystalline
Device for non-linear optical.
Background technique
Crystal with nonlinear optical effect is known as nonlinear optical crystal.Here nonlinear optical effect refers to again
Frequently with frequency, difference frequency, parameter amplification etc. effects.Only the crystal without symmetrical centre has been likely to nonlinear optical effect.Benefit
With the nonlinear optical effect of crystal, second harmonic generator, upper and lower frequency converter, optical parametric oscillator etc. can be made
Device for non-linear optical.The laser that laser generates can carry out frequency conversion by device for non-linear optical, to obtain more
The laser of useful wavelength, makes laser be more widely used.According to the difference of material application band, ultraviolet light can be divided into
Area, visible and near-infrared region and mid-infrared light area nonlinear optical material three categories.Visible region and ultraviolet region it is non-
Linear optical crystal material has been able to satisfy the requirement of practical application；It is such as practical in two frequencys multiplication (532nm) crystal mainly to have
KTP(KTiOPO4)、BBO(β-SnB2O4)、LBO(LiB3O5) crystal；In frequency tripling (355nm) crystal it is practical have BBO,
LBO、CBO(CsB3O5) available.And the nonlinear crystal development of infrared band is slow；The material of infrared light district is mostly
ABC2The chalcopyrite structure semiconductor material of type, such as AgGaQ2(Q=S, Se, Te), the light injury threshold of infrared non-linear crystal is too
Low and crystal growth is difficult, directly affects actual use.Middle infrared band nonlinear optical crystal has in optoelectronic areas
Important application, for example, it can by the means such as optical parametric oscillation or optically erasing by the laser of near infrared band (such as
1.064 μm) extend to middle infrared；It can also be with important laser (such as CO of centering infrared light district2Laser, 10.6 μm) it carries out again
Frequently, this is of great significance for obtaining the continuously adjustable laser of wavelength.Therefore the novel infrared non-linear of excellent performance is found
Optical crystal material has become one of difficult point and forward position direction of current nonlinear optical material research field.
Summary of the invention
It is an object of that present invention to provide a kind of Hg2GeSe4The preparation method of nonlinear optical crystal, another mesh of the invention
Be Hg is provided2GeSe4The purposes of nonlinear optical crystal.
The present invention provides a kind of Hg2GeSe4Nonlinear optical crystal, the Hg2GeSe4Nonlinear optical crystal does not have
Symmetrical centre is had, tetragonal crystal system, space group I are belonged to4 -, cell parameter are as follows: α=β
=γ=90 °, Z=2.
The Hg is prepared the present invention also provides a kind of2GeSe4The method of nonlinear optical crystal, this method pass through high temperature
Melt spontaneous crystallization method grows Hg2GeSe4Nonlinear optical crystal, comprising the following steps:
There to be composition to be equal to Hg2GeSe4Mixture or powdered Hg2GeSe4Compound is heated to melting high
Warm melt and after being kept for 24-96 hours, is cooled to room temperature with 1-10 DEG C/h of rate of temperature fall, obtains Hg2GeSe4Crystal.
Preferably, the composition is equal to Hg2GeSe4Mixture include Hg source material and Ge source material；The source Hg material
Material is Hg or HgSe；The Ge source material is Ge, GeSe or GeSe2。
Preferably, described to be equal to Hg2GeSe4Mixture further include Se simple substance.
The Hg is prepared the present invention also provides a kind of2GeSe4The method of nonlinear optical crystal, this method are under crucible
Drop method grows Hg2GeSe4Nonlinear optical crystal, specifically includes the following steps:
There to be composition to be equal to Hg2GeSe4Mixture or powdered Hg2GeSe4Compound is put into crystal growth dress
In setting, be to slowly warm up to melting sources, after raw material is completely melt, crystal growing apparatus with the speed of 0.1-10mm/h it is vertical under
Drop carries out Hg during crystal growing apparatus decline2GeSe4Nonlinear optical crystal growth, growth cycle are 5-20 days.
Preferably, the composition is equal to Hg2GeSe4Mixture include Hg source material and Ge source material；The source Hg material
Material is Hg or HgSe；The Ge source material is Ge, GeSe or GeSe2。
Preferably, described to be equal to Hg2GeSe4Mixture further include Se simple substance.
It is used to prepare the Hg2GeSe4The powdered Hg of nonlinear optical crystal2GeSe4The preparation process of compound includes
Following steps:
By Hg source material, Ge source material and simple substance Se according to molar ratio Hg:Ge:Se=2:1:4 ratio after mixing,
Being heated to 400-550 DEG C of progress solid phase reaction (in principle, can prepare Hg using general chemical synthesis process2GeSe4Chemical combination
Object；The preferred solid reaction process of the present invention), obtaining chemical formula is Hg2GeSe4Compound, smashed to pieces and grind powdered
Hg2GeSe4Compound；
The Hg source material can be Hg or HgSe；
The Ge source material can be Ge, GeSe or GeSe2。
The Hg2GeSe4Compound can be prepared by following chemical equations:
(1) 2Hg+Ge+4Se=Hg2GeSe4；
(2) 2Hg+GeSe+3Se=Hg2GeSe4；
(3)2Hg+GeSe2+ 2Se=Hg2GeSe4；
(4) 2HgSe+Ge+4Se=Hg2GeSe4；
(5) 2HgSe+GeSe+Se=Hg2GeSe4；
(6)2HgSe+GeSe2=Hg2GeSe4。
Hg having a size of Centimeter Level can get using above two method2GeSe4Nonlinear optical crystal；Use big ruler
Very little crucible, and extend growth period, then it can get corresponding larger size Hg2GeSe4Nonlinear optical crystal.
According to the crystallography data of crystal, crystal boule is oriented, is cut by required angle, thickness and sectional dimension brilliant
Body polishes crystal light pass surface, can be used as device for non-linear optical use, the Hg2GeSe4Nonlinear optical crystal has non-
Linear optics effect is big, transparency range is wide, physical and chemical performance is stable, and hardness is larger, good mechanical property, not easily broken, is easy to
The advantages that processing and preservation.
The present invention also provides Hg prepared by the preparation method2GeSe4Nonlinear optical crystal is preparing nonlinear optical
Learn the application in device.
The present invention still further provides a kind of device for non-linear optical, and the device for non-linear optical includes above-mentioned
Hg2GeSe4Nonlinear optical crystal.Hg2GeSe4Nonlinear optical crystal can be used for preparing device for non-linear optical, this is non-linear
Optical device includes that at least a branch of incidence electromagnetic radiation is passed through at least one piece of Hg2GeSe4Generated after nonlinear optical crystal to
Few a branch of frequency is different from the device of the output radiation of incidence electromagnetic radiation.
The present invention prepares Hg2GeSe4Crystal is easily grown up and uniformly without package, tool in the growth course of nonlinear optical crystal
Have that the speed of growth is very fast, at low cost, the advantages that being easy to get larger size crystal；Hg obtained2GeSe4Non-linear optical crystal
Body, which has, compares that nonlinear optical effect is big, transmission region is wide, and hardness is larger, good mechanical property, not easily broken and deliquesce, be easy to
The advantages that processing and preservation；The Hg2GeSe4Nonlinear optical crystal can be used for making device for non-linear optical.
Detailed description of the invention
Fig. 1 is using Hg of the present invention2GeSe4A kind of typical device for non-linear optical made of nonlinear optical crystal
Working principle diagram, wherein 1 is laser, 2 be incoming laser beam, and 3 be the Hg after crystal post-processing and optical manufacturing2GeSe4It is non-
Linear optical crystal, 4 be generated shoot laser beam, and 5 be filter plate.
Fig. 2 is Hg2GeSe4The structural schematic diagram of nonlinear optical crystal.
Specific embodiment
Any feature is disclosed to obtain in this specification, it unless specifically stated, can be equivalent or with similar purpose by other
Alternative features are replaced.Unless specifically stated, each feature is an example in a series of equivalent or similar characteristics
?.It is described to understand the present invention just for the sake of help, it should not be considered as to concrete restriction of the invention.
With the drawings and specific embodiments, the present invention is described in further detail below.
Embodiment 1: Hg is prepared using high-temperature fusant spontaneous crystallization method2GeSe4Crystal:
Weigh 5.591 grams of HgSe and 2.306 gram of GeSe2(i.e. HgSe:GeSe2=0.02mol:0.01mol), uniformly mix
Afterwards, it is fitted into the quartz glass tube of Φ 12mm × 200mm, is evacuated to 10-3After pa, tubular type growth is packaged and placed on oxyhydrogen flame
In furnace, 750 DEG C are slowly increased to, constant temperature 72 hours, with the rate slow cooling of 3 DEG C/h to room temperature, closes tubular type growth furnace；To stone
It is cut after English pipe is cooling, the Hg of φ 20x60mm black can be obtained2GeSe4Crystal.
Embodiment 2: Hg is prepared using Bridgman-Stockbarger method2GeSe4Crystal:
Weigh 11.182 grams of HgSe and 4.612 gram of GeSe2(i.e. Hg:Ge:Se=0.04mol:0.02mol:0.08mol),
After evenly mixing, it is fitted into the quartz glass tube of Φ 25mm × 200mm, is evacuated to 10-3After pa, it is packaged and placed on oxyhydrogen flame
In crystal growing furnace, being slowly increased to 750 DEG C makes melting sources, and after raw material is completely melt, grower was with 0.1-10mm/ hours
Speed vertically decline；After crystal growth, grower was down to room temperature with 75 hours, obtained φ 30x90mm black
Hg2GeSe4Crystal.
After tested, Hg prepared by above-described embodiment 1-22GeSe4Nonlinear optical crystal category tetragonal crystal system, space group are
I4 -, cell parameter are as follows:α=β=γ=90 °, Z=2, Tool
There is frequency-doubled effect, transparency range is 1-20 μm；Fig. 2 is the Hg2GeSe4The structural schematic diagram of nonlinear optical crystal.
Embodiment 3:
The resulting Hg of embodiment 1-22GeSe4Crystal is not easily broken, is not easy to deliquesce, easy to cut, polishing and preservation.
By the resulting Hg of embodiment 1-22GeSe4Crystal is placed at position of 1 shown device of attached drawing marked as 3, at room temperature, with tune Q
Ho:Tm:Cr:YAG laser light source, incident wavelength be 2090nm infrared light, output wavelength be 1045nm frequency doubled light,
Laser intensity is AgGaSe under the same terms22.1 times.
Attached drawing 1 is using Hg of the present invention2GeSe4A kind of typical device for non-linear optical made of nonlinear optical crystal
Working principle diagram, wherein 1 is laser, 2 be incoming laser beam, and 3 be the AgZnPS after crystal post-processing and optical manufacturing4
Nonlinear optical crystal, 4 be generated shoot laser beam, and 5 be filter plate；Incoming laser beam 2 is issued by laser 1 to inject
Hg2GeSe4Monocrystal 3, generated shoot laser beam 4 is by filter plate 5, and laser beam required for obtaining.
Use Hg of the invention2GeSe4The device of nonlinear optical crystal production can be a times frequency generator, upper and lower frequency
Converter, optical parametric oscillator.Photoparametric amplifier etc..
It should be noted last that the above examples are only used to illustrate the technical scheme of the present invention and are not limiting.Although ginseng
It is described the invention in detail according to embodiment, it will be apparent to an ordinarily skilled person in the art that technical side of the invention
Case is modified or replaced equivalently, and without departure from the spirit and scope of technical solution of the present invention, should all be covered in the present invention
Scope of the claims in.
Claims (9)
1. a kind of Hg2GeSe4The preparation method of nonlinear optical crystal, the preparation method comprises the following steps:
Using high-temperature fusant spontaneous crystallization method or Bridgman-Stockbarge method for growing Hg2GeSe4Nonlinear optical crystal.
2. Hg according to claim 12GeSe4The preparation method of nonlinear optical crystal, which is characterized in that the high temperature
Melt spontaneous crystallization method grows Hg2GeSe4Nonlinear optical crystal the following steps are included:
There to be composition to be equal to Hg2GeSe4Mixture or powdered Hg2GeSe4Compound is heated to melting to obtain high temperature solution
And after being kept for 24-96 hours, room temperature is cooled to 1-10 DEG C/h of rate of temperature fall, obtains Hg2GeSe4Non-linear optical crystal
Body.
3. Hg according to claim 22GeSe4The preparation method of nonlinear optical crystal, which is characterized in that the composition
It is equal to Hg2GeSe4Mixture include Hg source material, Ge source material and Se simple substance；
The Hg source material is Hg or HgSe；
The Ge source material is Ge, GeSe or GeSe2。
4. Hg according to claim 12GeSe4The preparation method of nonlinear optical crystal, which is characterized in that the crucible
Descent method for growing Hg2GeSe4Nonlinear optical crystal the following steps are included:
There to be composition to be equal to Hg2GeSe4Mixture or powdered Hg2GeSe4Compound is put into crystal growing apparatus, is delayed
Slowly melting sources are warming up to, after raw material is completely melt, crystal growing apparatus is vertically declined with the speed of 0.1-10mm/h, in crystalline substance
Hg is carried out during the decline of body grower2GeSe4Nonlinear optical crystal growth, growth cycle are 5-20 days.
5. Hg according to claim 42GeSe4The preparation method of nonlinear optical crystal, which is characterized in that the composition
It is equal to Hg2GeSe4Mixture include Hg source material, Ge source material and Se simple substance；
The Hg source material is Hg or HgSe；
The Ge source material is Ge, GeSe or GeSe2。
6. according to the described in any item Hg of claim 2-52GeSe4The preparation method of nonlinear optical crystal, which is characterized in that
The powdered Hg2GeSe4The preparation method of compound the following steps are included:
By Hg source material, Ge source material and simple substance Se according to molar ratio Hg:Ge:Se=2:1:4 ratio after mixing, heating
It is reacted to 400-550 DEG C, obtaining chemical formula is Hg2GeSe4Compound, smashed to pieces and grind to obtain powdered Hg2GeSe4's
Compound.
7. Hg according to claim 62GeSe4The preparation method of nonlinear optical crystal, which is characterized in that the source Hg
Material is Hg or HgSe；The Ge source material is Ge, GeSe or GeSe2。
8. Hg prepared by any one of the claim 1-7 preparation method2GeSe4Nonlinear optical crystal prepare it is non-linear
Application in optical device.
9. a kind of device for non-linear optical, which is characterized in that the optical device includes the preparation side any one of claim 1-7
Hg prepared by method2GeSe4Nonlinear optical crystal.
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101767778A (en) * | 2010-02-03 | 2010-07-07 | 中国科学院理化技术研究所 | BaCa4Se7 compound, BaCa4Se7 nonlinear optical crystal, preparation method and application |
| CN105113005A (en) * | 2015-07-07 | 2015-12-02 | 中国科学院理化技术研究所 | BaHgSe2 nonlinear optical crystal, and preparation method and use thereof |
-
2018
- 2018-04-04 CN CN201810297506.1A patent/CN109137081A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101767778A (en) * | 2010-02-03 | 2010-07-07 | 中国科学院理化技术研究所 | BaCa4Se7 compound, BaCa4Se7 nonlinear optical crystal, preparation method and application |
| CN105113005A (en) * | 2015-07-07 | 2015-12-02 | 中国科学院理化技术研究所 | BaHgSe2 nonlinear optical crystal, and preparation method and use thereof |
Non-Patent Citations (1)
| Title |
|---|
| YONGKWAN DONG, ET AL.: "Reinvestigation of Hg2GeSe4 based on single-crystal data", 《ACTA CRYST.》 * |
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