CN107021462A - Selenium gallium zinc barium compound, selenium gallium zinc barium infrared nonlinear optical crystal and its production and use - Google Patents
Selenium gallium zinc barium compound, selenium gallium zinc barium infrared nonlinear optical crystal and its production and use Download PDFInfo
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- CN107021462A CN107021462A CN201710278934.5A CN201710278934A CN107021462A CN 107021462 A CN107021462 A CN 107021462A CN 201710278934 A CN201710278934 A CN 201710278934A CN 107021462 A CN107021462 A CN 107021462A
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B19/00—Selenium; Tellurium; Compounds thereof
- C01B19/002—Compounds containing, besides selenium or tellurium, more than one other element, with -O- and -OH not being considered as anions
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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
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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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- 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
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
- C01P2002/77—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by unit-cell parameters, atom positions or structure diagrams
Abstract
The invention discloses a kind of selenium gallium zinc barium compound, chemical formula is Ba5ZnGa6Se15.The invention also discloses the preparation method of selenium gallium zinc barium compound.In addition, the invention also discloses a kind of selenium gallium zinc crystal of barium and its preparation method and application.In the growth of the selenium gallium zinc barium infrared nonlinear optical crystal of the present invention, crystal is easily grown up and without parcel, has the advantages that the speed of growth is very fast, cost is low, be readily available large-size crystal；The selenium gallium zinc barium infrared nonlinear optical crystal obtained has the advantages that relatively wide infrared light transmission wave band, good mechanical property, easy to process and preservation；The selenium gallium zinc crystal of barium can be used for making infrared laser frequency conversion device.
Description
Technical field
The present invention relates to inorganic compound field of material technology, and in particular to selenium gallium zinc barium compound and preparation method thereof,
Selenium gallium zinc barium infrared nonlinear optical crystal and its preparation method and application.
Background technology
Second-order non-linear optical crystal is a class combines closely with laser technology, important photoelectric functional material, such
Crystal can realize the tune to commodity laser frequency by nonlinear effects such as frequency multiplication, difference frequency and frequency and optical parametric oscillators
Section, produces laser with new wavelength source, and then greatly expands the application of laser., can be by for example using suitable frequency-doubling crystal
Nd:YAG (output wavelength is 1064nm) laser freuqency doubling, produces the laser that wavelength is 532nm；2.1 μm of laser is after frequency multiplication
The laser that wavelength is 1.05 μm can be produced.
At present, in Uv and visible light wave band, it was found that a series of outstanding nonlinear optical crystals, including KBBF
(KBe2BO3F2)、BBO(β-BaB2O4)、LBO(LiB3O5)、CBO(CsB3O5)、KDP(KH2PO4) and KTP (KTiOPO4) etc., it
Have been obtained for being widely applied in terms of new Uv and visible light wave band of laser is produced and disclosure satisfy that various using will
Ask.However, still relatively deficient to the research of infrared band nonlinear optical crystal, can practical crystal only have ZGP
(ZnGeP2)、AGS(AgGaS2) and AGSe (AgGaSe2) etc. it is few in number several；These other crystal also exist serious
There is big anisotropic thermal expansion in shortcoming, such as AGS and AGSe, high quality large size crystal growth is difficult；Thermal conductivity is low,
Stronger thermal gradient and thermal lensing effect can be produced during high power pump causes laser damage threshold extremely low, it is impossible to be used in high power
Infrared laser is exported；ZGP crystal is the current optimal material for producing 3~5 μm of infrared lasers, but its crystal growth is extremely tired
Difficulty, and there is inevitable, serious residual absorption so that its laser that must be more than 2 μm using wavelength enters near infrared region
Row pumping.The practical application for limiting above-mentioned infrared crystal of disadvantage mentioned above seriously；In addition, in 8~12 μm of infrared bands still
Lack the nonlinear crystalline material of function admirable.And the novel infrared non-linear crystal BGS (BaGa found in the recent period4S7) and BGSe
(BaGa4Se7) the development in laboratory stage is still within, specific actual use value needs further further investigation with application band.
Therefore, explore have be easy to grow, be machined property well, high laser damage threshold, infrared non-linear it is excellent
Novel crystal seem particularly urgent, be also one of the study hotspot and difficult point in current nonlinear optical material field.Chalcogenide
Compound has the advantages that infrared transmission scope is wide and nonlinear factor ratio is larger, is that novel infrared nonlinear optical crystal is explored
Main study subject.For Ba/Zn/Ga/Se quaternary systems, research report is had no at present, and the present invention is the first sulfur family of the system
Report of the compound in terms of FTIR radiation transmittance.
The content of the invention
Present invention aim to address above-mentioned prior art problem, there is provided a kind of selenium gallium zinc barium compound and its preparation side
Method, selenium gallium zinc barium infrared nonlinear optical crystal and its preparation method and application.
In order to reach above-mentioned technique effect, the present invention takes following technical scheme：
A kind of selenium gallium zinc barium compound, the chemical formula of the selenium gallium zinc barium compound is Ba5ZnGa6Se15。
The preparation method of above-mentioned selenium gallium zinc barium compound, comprises the following steps：
The Ba that the present invention is provided5ZnGa6Se15The preparation method of compound, its step is as follows：
After Ba materials, material containing Zn, material containing Ga and simple substance Se dispensings will be contained and be well mixed, 800~900 DEG C are heated to
High temperature solid state reaction is carried out, selenium gallium zinc barium compound is obtained；
All Ba in the material containing Ba, material containing Zn, material containing Ga and simple substance Se:Zn:Ga:Se elemental mole ratios are
5:1:6:15；
The material containing Ba is barium simple substance or barium selenide；The material containing Zn is ternary compound selenium gallium zinc ZnGa2Se4；Institute
Material containing Ga is stated for gallium simple substance or the gallium of three selenizing two.
According to the present invention further technical scheme, it is described be heated to 800~900 DEG C and carry out high temperature solid state reactions be
Refer to：
Well mixed material is fitted into quartz ampoule, 10 then are evacuated to quartz ampoule-3Pa simultaneously carries out fusing sealed knot；
The quartz ampoule of sealed knot is put into Muffle furnace, 800~900 DEG C are warming up to 30~50 DEG C/h speed, 96h is incubated, after cooling
Sample is taken out, is again placed in quartz ampoule being evacuated to 10 after being ground the sample of taking-up-3Pa simultaneously carries out fusing sealed knot, it
After be put into Muffle furnace be warming up to 800 DEG C sintering 48h；Sample is taken out and ground and obtains powdered Ba5ZnGa6Se15Chemical combination
Thing.
A kind of selenium gallium zinc crystal of barium, it is characterised in that the chemical formula of the crystal is Ba5ZnGa6Se15, the crystal is infrared
Nonlinear optical crystal, the crystal is non-centrosymmetric structure, belongs to rhombic system, space group is Ama2, and its cell parameter is： α=β=γ=90 °,Z
=4.
The preparation method of above-mentioned selenium gallium zinc crystal of barium, it comprises the following steps：Selenium gallium zinc barium compound is placed in temperature
Gradient for 5~10 DEG C/cm crystal growing furnace in, prepare selenium gallium zinc barium using horizontal gradient condensation method or Bridgman-Stockbarger method
Crystal.
According to the present invention further technical scheme, the horizontal gradient condensation method refers to powdered selenium gallium zinc barium
Compound is enclosed after silica crucible, is put into horizontal crystal growth stove；It is heated to compound melts and keeps after 24~72h, with 5~
10mm/d speed movement thermal field, after crystal growth terminates, is down to room temperature with 10~30 DEG C/h rate of temperature fall, obtains yellow saturating
Bright selenium gallium zinc crystal of barium.
According to the present invention further technical scheme, the Bridgman-Stockbarger method refers to powdered selenium gallium zinc barium compound
Enclose after silica crucible, be put into crystal growing furnace；Be to slowly warm up to compound melts, treat powder be completely melt and keep 24~
After 72h, silica crucible is vertically declined with 0.3~2.0mm/h speed, and selenium gallium zinc crystal of barium is carried out during crucible decline
Growth, room temperature is down to after crystal growth terminates with 10~30 DEG C/h rate of temperature fall, and its growth cycle is 10~30d.
Above-mentioned selenium gallium zinc crystal of barium is used to prepare infrared laser frequency conversion device.
The present invention is will be described in detail below.
In the present invention, chemical formula is Ba5ZnGa6Se15Selenium gallium zinc barium compound, its prepare some related chemistries reaction
Formula includes：
The Ba5ZnGa6Se15Compound is successfully prepared by following chemical equations：
(1)5BaSe+ZnGa2Se4+2Ga2Se3=Ba5ZnGa6Se15；
(2)5BaSe+ZnGa2Se4+ 4Ga+6Se=Ba5ZnGa6Se15；
(3)5Ba+ZnGa2Se4+2Ga2Se3+ 5Se=Ba5ZnGa6Se15；
(4)5Ba+ZnGa2Se4+ 4Ga+11Se=Ba5ZnGa6Se15；
The crystal structure of the selenium gallium zinc barium compound is as shown in figure 1, be a kind of three-dimensional frame structure：Zn and Ga are with 1:6
Ratio unity of possession structure in tetrahedral coordination position, these (Zn/Ga) Se4The mutual concurrent of tetrahedron connects to form three-dimensional
Framework, Ba ions are located in the space of framework.
The present invention prepares selenium gallium zinc crystal of barium using horizontal gradient condensation method or Bridgman-Stockbarger method can obtain size for cm
The Ba of level5ZnGa6Se15Infrared nonlinear optical crystal；Using larger-sized crucible, while extending growth cycle, then it can obtain
Obtain corresponding large-size Ba5ZnGa6Se15Infrared nonlinear optical crystal.
After high quality large size crystal is obtained, the crystal of growth can be carried out according to the crystallographic characteristics of the crystal
Orientation；Afterwards, can be by required angle, thickness and sectional dimension sliced crystal；Finally mirror polish by thang-kng of quartz crystal device simultaneously
Plated film, that is, complete the preparation of the crystal infrared laser frequency conversion device.Ba5ZnGa6Se15Crystal have physical and chemical performance it is stable,
Good mechanical property, be difficult deliquescence, it is easy to process and preserve the advantages of；The present invention furthermore provides Ba5ZnGa6Se15It is infrared non-
The purposes of linear optical crystal, the Ba5ZnGa6Se15Crystal is used to prepare infrared laser frequency conversion device, and the device is included will at least
A branch of incident laser passes through at least one piece Ba5ZnGa6Se15The radiation that at least a branch of frequency is different from incident laser is produced after crystal
The device of output.
The present invention compared with prior art, with following beneficial effect：
Effect of the invention is that being Ba there is provided a kind of chemical formula5ZnGa6Se15Novel infrared nonlinear optical crystal and
Preparation method and use.Easily grown up in the growing crystals of the selenium gallium zinc barium infrared nonlinear optical crystal and without parcel, tool
Have the advantages that the speed of growth is very fast, cost is low, be readily available large-size crystal；The selenium gallium zinc barium infrared non-linear light obtained
Learning crystal has the advantages that relatively wide infrared light transmission wave band, good mechanical property, easy to process and preservation；The selenium gallium zinc crystal of barium
Available for making infrared laser frequency conversion device.
Brief description of the drawings
Fig. 1 is the structural representation of selenium gallium zinc barium infrared nonlinear optical crystal prepared by the present invention.
Fig. 2 is that a kind of work for the typical infrared nonlinear optical device being made of selenium gallium zinc crystal of barium of the present invention is former
Reason figure.
Embodiment
With reference to embodiments of the invention, the invention will be further elaborated.
Embodiment 1
Using 5BaSe+ZnGa2Se4+2Ga2Se3=Ba5ZnGa6Se15Reaction equation prepares selenium gallium zinc with high-temperature solid phase reaction method
Barium compound；
The BaSe is 10.815 grams, the ZnGa2Se4For 5.207 grams, the Ga2Se3For 7.527 grams；That is BaSe:
ZnGa2Se4:Ga2Se3=0.05mol:0.01mol:0.02mol；
Concrete operation step is to weigh reagent respectively by above-mentioned dosage in glove box, place them into mortar, mixing
And grind, in the quartz ampoule for being then charged into Φ 19mm × 25mm, it is evacuated to 10-3Quartz ampoule is melted with oxyhydrogen flame after Pa and sealed
Dress, is put into Muffle furnace, and 800 DEG C are risen to 50 DEG C/h heating rate, is incubated 96h, sample is taken out after cooling, to the sample of taking-up
Product are again placed in quartz ampoule being evacuated to 10 after being ground-3Pa simultaneously carries out fusing sealed knot, and heating in Muffle furnace is put into afterwards
To 800 DEG C of sintering 48h；Sample is taken out and ground and obtains powdered Ba5ZnGa6Se15Compound.
Embodiment 2
Using 5BaSe+ZnGa2Se4+ 4Ga+6Se=Ba5ZnGa6Se15Reaction equation prepares selenium gallium with high-temperature solid phase reaction method
Zinc barium compound；
The BaSe is 10.815 grams, the ZnGa2Se4For 5.207 grams, the Ga is 2.789 grams, and the Se is 4.738
Gram；That is BaSe:ZnGa2Se4:Ga:Se=0.05mol:0.01mol:0.04mol:0.06mol；
Concrete operation step is to weigh reagent respectively by above-mentioned dosage in glove box, they are mixed, be then charged into Φ
In 19mm × 25mm quartz ampoule, 10 are evacuated to-3Quartz ampoule is melted with oxyhydrogen flame after Pa and encapsulated, is put into Muffle furnace, with
30 DEG C/h heating rate rises to 900 DEG C, is incubated 96h, sample is taken out after cooling, is put again after being ground to the sample of taking-up
10 are evacuated in quartz ampoule-3Pa simultaneously carries out fusing sealed knot, is put into afterwards in Muffle furnace and is warming up to 800 DEG C of sintering 48h；By sample
Product, which take out and ground, obtains powdered Ba5ZnGa6Se15Compound.
Embodiment 3
Using 5Ba+ZnGa2Se4+2Ga2Se3+ 5Se=Ba5ZnGa6Se15Reaction equation prepares selenium gallium with high-temperature solid phase reaction method
Zinc barium compound；
The Ba is 6.866 grams, the ZnGa2Se4For 5.207 grams, the Ga2Se3For 7.527 grams, the Se is
3.948 gram；That is BaSe:ZnGa2Se4:Ga2Se3:Se=0.05mol:0.01mol:0.02mol:0.05mol；
Its concrete operation step is to weigh reagent respectively by above-mentioned dosage in glove box, be loaded into Φ 19mm ×
In 25mm quartz ampoule, 10 are evacuated to-3Quartz ampoule is melted with flame after Pa and encapsulated, is put into Muffle furnace, is slowly increased to 850
DEG C, its heating rate is 40 DEG C/h, is incubated 96h, sample is taken out after cooling, and stone is again placed in after being ground to the sample of taking-up
Ying Guanzhong is evacuated to 10-3Pa simultaneously carries out fusing sealed knot, is put into afterwards in Muffle furnace and is warming up to 800 DEG C of sintering 48h；Sample is taken
Go out and grind and obtain powdered Ba5ZnGa6Se15Compound.
Embodiment 4
Selenium gallium zinc crystal of barium is prepared using horizontal gradient condensation method：
By the Ba obtained in embodiment 1 to 35ZnGa6Se15Powder is fitted into Φ 16mm × 20mm silica crucibles, vacuumizes
To 10-3(thermograde is 5~10 DEG C/cm) after Pa, is placed in horizontal growth stove after being encapsulated with oxyhydrogen flame, 980 DEG C are slowly increased to
Raw material is completely melt and is kept after 24~72h, thermal field is moved with 5~10mm/d speed, after crystal growth terminates, with 10
~30 DEG C/h rate of temperature fall is cooled to room temperature, obtains the Ba of yellow transparent5ZnGa6Se15Crystal.
Embodiment 5
Selenium gallium zinc crystal of barium is prepared using Bridgman-Stockbarger method：
By the Ba obtained in embodiment 1 to 35ZnGa6Se15Powder is fitted into Φ 16mm × 20mm silica crucibles, vacuumizes
To 10-3After Pa, it is placed in after being encapsulated with oxyhydrogen flame in crystal growing apparatus, being slowly increased to 980 DEG C makes raw material be completely melt and keep
After 24~72h, silica crucible is vertically declined with 0.3~2.0mm/h speed, is carried out during crucible decline
Ba5ZnGa6Se15Infrared nonlinear optical crystal is grown, and after crystal growth terminates, room is cooled to 10~30 DEG C/h speed
Temperature, obtains the Ba of yellow transparent5ZnGa6Se15Crystal.
After tested, the Ba prepared by above-described embodiment 4 and 55ZnGa6Se15The nonlinear optics crystal is non-centrosymmetry
Structure, belongs to rhombic system, space group is Ama2, and its cell parameter is： α=β=γ=90 °,Z=4；The crystal has infrared powder SHG effect；Fig. 1 is this
Ba5ZnGa6Se15The structural representation of infrared nonlinear optical crystal, is a kind of three-dimensional frame structure：Zn and Ga are with 1:6 ratio
The position of tetrahedral coordination in rate unity of possession structure, these (Zn/Ga) Se4The mutual concurrent of tetrahedron connects to form three-dimensional box
Frame, Ba ions are located in the space of framework.
Embodiment 6
By the Ba of the gained of embodiment 4 and 55ZnGa6Se15Crystal be oriented, cut, polishing and plated film after, be placed on accompanying drawing 2
At position of the shown device marked as 4, at room temperature, with the Ho for adjusting Q:Tm:Cr:YAG laser makees light source, and incident wavelength is
2090nm infrared light, output wavelength is 1045nm frequency doubled light.
Accompanying drawing 2 is to use Ba of the present invention5ZnGa6Se15It is a kind of typical infrared non-that infrared nonlinear optical crystal is made
The fundamental diagram of linear optics device, including infrared laser 1；What infrared laser 1 was produced will incide crystal
On laser beam 2；Flashlight and ideler frequency light that laser beam 2 is produced through the mirror 3 for having plated film, total reflection crystal；By crystal
The Ba for meeting laser wavelength of incidence phase-matching condition after post processing and optical manufacturing5ZnGa6Se15Crystal 4；The mirror of film is plated
Flashlight and ideler frequency light that son 5 can be produced partly through crystal, are totally reflected incoming laser beam 2；The required laser obtained
Beam 6,7.
Although reference be made herein to invention has been described for explanatory embodiment of the invention, and above-described embodiment is only this hair
Bright preferably embodiment, embodiments of the present invention are simultaneously not restricted to the described embodiments, it should be appreciated that people in the art
Member can be designed that a lot of other modification and embodiment, and these modifications and embodiment will fall in principle disclosed in the present application
Within scope and spirit.
Claims (9)
1. a kind of selenium gallium zinc barium compound, it is characterised in that the chemical formula of the selenium gallium zinc barium compound is Ba5ZnGa6Se15。
2. the preparation method of selenium gallium zinc barium compound described in claim 1, it is characterised in that comprise the following steps：
To contain Ba materials, material containing Zn, material containing Ga and simple substance Se it is well mixed after, be heated to 800~900 DEG C and carry out high temperature consolidating
Phase reaction, obtains selenium gallium zinc barium compound；
In the material containing Ba, material containing Zn, material containing Ga and simple substance Se, all Ba:Zn:Ga:Se elemental mole ratios are 5:
1:6:15。
3. the preparation method of selenium gallium zinc barium compound according to claim 2, it is characterised in that：
The material containing Ba is barium simple substance or barium selenide；The material containing Zn is ternary compound selenium gallium zinc ZnGa2Se4；It is described to contain
Ga materials are gallium simple substance or the gallium of three selenizing two.
4. the preparation method of selenium gallium zinc barium compound according to claim 3, it is characterised in that：
It is described be heated to 800~900 DEG C carry out high temperature solid state reactions refer to：
Well mixed material is fitted into quartz ampoule, 10 then are evacuated to quartz ampoule-3Pa simultaneously carries out fusing sealed knot；Will envelope
The quartz ampoule of knot is put into Muffle furnace, and 800~900 DEG C are warming up to 30~50 DEG C/h speed, is incubated 96h, is taken out after cooling
Sample, is again placed in quartz ampoule being evacuated to 10 after being ground the sample of taking-up-3Pa simultaneously carries out fusing sealed knot, Zhi Houfang
Enter to be warming up to 800 DEG C of sintering 48h in Muffle furnace；Sample is taken out and ground and obtains powdered Ba5ZnGa6Se15Compound.
5. a kind of selenium gallium zinc crystal of barium, it is characterised in that：The chemical formula of the crystal is Ba5ZnGa6Se15, the crystal is infrared
Nonlinear optical crystal, the crystal is non-centrosymmetric structure, belongs to rhombic system, space group is Ama2, and cell parameter is：α=β=γ=90 °, Z
=4.
6. the preparation method of selenium gallium zinc crystal of barium described in claim 5, it is characterised in that comprise the following steps：
Selenium gallium zinc barium compound described in claim 1 is placed in the crystal growing furnace that thermograde is 5~10 DEG C/cm, profit
Selenium gallium zinc crystal of barium is prepared with horizontal gradient condensation method or Bridgman-Stockbarger method.
7. the preparation method of selenium gallium zinc crystal of barium according to claim 6, it is characterised in that：
The horizontal gradient condensation method refers to enclose powdered selenium gallium zinc barium compound after silica crucible, is put into level crystal life
In long stove；It is heated to compound melts and keeps after 24~72h, thermal field is moved with 5~10mm/d speed, crystal growth knot is treated
Shu Hou, room temperature is down to 10~30 DEG C/h rate of temperature fall, obtains the selenium gallium zinc crystal of barium of yellow transparent.
8. the preparation method of selenium gallium zinc crystal of barium according to claim 6, it is characterised in that：
The Bridgman-Stockbarger method refers to enclose powdered selenium gallium zinc barium compound after silica crucible, is put into crystal growing furnace；
Compound melts are to slowly warm up to, after powder is completely melt and is incubated after 24~72h, silica crucible is with 0.3~2.0mm/h's
Speed vertically declines, and the growth of selenium gallium zinc crystal of barium is carried out during crucible decline, after crystal growth terminates, with 10~30
DEG C/h rate of temperature fall is down to room temperature, obtains the selenium gallium zinc crystal of barium of yellow transparent, growth cycle is 10~30d.
9. the application of selenium gallium zinc crystal of barium described in claim 5, it is characterised in that：
The selenium gallium zinc crystal of barium is used to prepare infrared laser frequency conversion device, and prepared laser frequency device is comprising will at least one
Beam incident laser is different from the radiant output of incident laser by producing at least a branch of frequency after at least one piece selenium gallium zinc crystal of barium
Device.
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| CN108441955A (en) * | 2018-04-23 | 2018-08-24 | 中国科学院福建物质结构研究所 | Infrared nonlinear optical crystal, preparation method and purposes |
| CN109137080A (en) * | 2018-01-26 | 2019-01-04 | 中国科学院理化技术研究所 | A kind of method of selenium gallium crystal of barium growth |
| CN109722707A (en) * | 2019-03-14 | 2019-05-07 | 中国科学院福建物质结构研究所 | A kind of monocrystal material, preparation method and its application |
| CN109750357A (en) * | 2017-11-08 | 2019-05-14 | 青岛科技大学 | Infrared nonlinear optical crystal Ba10Zn7M6Q26And preparation method thereof and purposes |
| CN109853039A (en) * | 2019-02-01 | 2019-06-07 | 中国科学院福建物质结构研究所 | A kind of monocrystal material Ba13In12Zn7S38Preparation method and applications |
| CN110284196A (en) * | 2019-07-24 | 2019-09-27 | 中国科学院福建物质结构研究所 | One kind material containing crystalline lithium and its preparation method and application |
| CN111334866A (en) * | 2018-12-18 | 2020-06-26 | 中国科学院福建物质结构研究所 | Co-crystal, preparation method and application thereof |
| CN111334848A (en) * | 2018-12-18 | 2020-06-26 | 中国科学院福建物质结构研究所 | Single crystal material, preparation method and application thereof |
| CN115535972A (en) * | 2022-10-13 | 2022-12-30 | 天津理工大学 | Alkaline earth metal zinc gallium tin chalcogenide and alkaline earth metal zinc gallium tin chalcogenide nonlinear optical crystal, and preparation method and application thereof |
| CN115991500A (en) * | 2021-10-19 | 2023-04-21 | 天津理工大学 | Chalcogenium lithopone compound, chalcogenium lithopone nonlinear optical crystal, preparation method and application |
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