CN105506743B - A kind of Li6Cd5Sn4Se16Nonlinear optical crystal and its preparation method and purposes - Google Patents

A kind of Li6Cd5Sn4Se16Nonlinear optical crystal and its preparation method and purposes Download PDF

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CN105506743B
CN105506743B CN201511020624.0A CN201511020624A CN105506743B CN 105506743 B CN105506743 B CN 105506743B CN 201511020624 A CN201511020624 A CN 201511020624A CN 105506743 B CN105506743 B CN 105506743B
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nonlinear optical
optical crystal
crystal
source materials
compound
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CN105506743A (en
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姚吉勇
李小双
李超
周墨林
吴以成
陈创天
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Technical Institute of Physics and Chemistry of CAS
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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
    • 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 present invention relates to Li6Cd5Sn4Se16Nonlinear optical crystal and preparation method and purposes；The Li6Cd5Sn4Se16Nonlinear optical crystal does not possess and has symmetrical centre, belongs to rhombic system, space group Pna21, its cell parameter is：α=β=γ=90 °；The nonlinear optical crystal uses high-temperature fusant spontaneous crystallization method or Bridgman-Stockbarge method for growing；The nonlinear optical crystal is in growth, and crystal is easily grown up and transparent no parcel, has the advantages that speed of growth is very fast, and cost is low, easily obtains large-size crystal；The advantages that nonlinear optical crystal has wider transmission region, and hardness is larger, good mechanical property, not easily broken and deliquescence, and easy processing is with preserving；The Li6Cd5Sn4Se16Nonlinear optical crystal can be used for making device for non-linear optical.

Description

A kind of Li6Cd5Sn4Se16Nonlinear optical crystal and its preparation method and purposes
Technical field
The invention belongs to nonlinear optical crystal, prepare and for field, more particularly to a kind of Li6Cd5Sn4Se16It is non-thread Property optical crystal (Li6Cd5Sn4Se16Monocrystalline) and the SnGa4Se7The preparation method of monocrystalline and the Li6Cd5Sn4Se16Monocrystalline is used for The purposes of the device for non-linear optical of making.
Background technology
Crystal with nonlinear optical effect is referred to as nonlinear optical crystal.Here nonlinear optical effect refers to again Frequently with frequency, difference frequency, parameter amplification etc. effect.Only the crystal without symmetrical centre has been only possible to nonlinear optical effect.Profit 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.Laser caused by laser can carry out frequency conversion by device for non-linear optical, more so as to obtain The laser of useful wavelength, makes laser be more widely used.According to the difference of materials application wave band, ultraviolet light can be divided into Area, visible and near-infrared region and mid-infrared light area nonlinear optical material three major types.Visible region and ultraviolet region it is non- Linear optical crystal material can meet 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；Can also centering infrared light district important laser (such as CO2Laser, 10.6 μm) carry out again Frequently, this is significant for the laser for obtaining wavelength continuously adjustabe.Therefore the novel infrared non-linear of premium properties is found Optical crystal material turns into one of difficult point and forward position direction of current nonlinear optical material research field.
We have studied Li first6Cd5Sn4Se16Crystal structure, and find Li6Cd5Sn4Se16With nonlinear optics Performance.
The content of the invention
Present invention aims at provide a kind of Li6Cd5Sn4Se16Nonlinear optical crystal.
Another object of the present invention is to provide Li6Cd5Sn4Se16The preparation method of nonlinear optical crystal.
Still a further object of the present invention is to provide Li6Cd5Sn4Se16The purposes of nonlinear optical crystal.
Technical scheme is as follows:
Li provided by the invention6Cd5Sn4Se16Nonlinear optical crystal, the Li6Cd5Sn4Se16Nonlinear optical crystal is not Possessing has symmetrical centre, belongs to rhombic system, space group Pna21, its cell parameter is： α=β=γ=90 °.
Li provided by the invention6Cd5Sn4Se16The preparation method of nonlinear optical crystal, it is high-temperature fusant spontaneous crystallization Method grows Li6Cd5Sn4Se16Nonlinear optical crystal, its step are：
By powdered Li6Cd5Sn4Se16Compound or according to mol ratio Li:Cd:Sn:Se=6:5:4:The mixing of 16 ratios Mixture is heated to melting to obtain high temperature solution, and 24-96 hours are kept under the high temperature solution state, afterwards, with 1-10 DEG C/it is small When rate of temperature fall be cooled to room temperature, obtain Li6Cd5Sn4Se16Crystal；
The powdered Li6Cd5Sn4Se16Preparing for compound is as follows:
By Li source materials, Cd source materials, Sn source materials and Se simple substance according to mol ratio Li:Cd:Sn:Se=6:5:4:16 Ratio it is well mixed after, be heated to 800-1050 DEG C of progress chemical synthesis, it is Li to obtain chemical formula6Cd5Sn4Se16Compound, Powdered Li is ground to obtain through smashing to pieces6Cd5Sn4Se16Compound；
The Li source materials are lithium simple substance or lithium selenide；
The Cd source materials are cadmium simple substance or cadmium selenide：
The Sn4Source material is tin simple substance or two stannic selenides.
Described chemical synthesis is solid phase reaction.
The powdered Li6Cd5Sn4Se16Compound is prepared according to the following reaction formula:
(1) 6Li+5Cd+4Sn+16Se=Li6Cd5Sn4Se16；
(2)3Li2Se+5Cd+4Sn+13Se=Li6Cd5Sn4Se16；
(3) 6Li+5CdSe+4Sn+11Se=Li6Cd5Sn4Se16；
(4)6Li+5Cd+4SnSe2+ 8Se=Li6Cd5Sn4Se16；
(5)3Li2Se+5CdSe+4SnSe2=Li6Cd5Sn4Se16；
Li provided by the invention6Cd5Sn4Se16Another preparation method of nonlinear optical crystal, it is Bridgman-Stockbarger method Grow Li6Cd5Sn4Se16Nonlinear optical crystal, its step are as follows：
By powdered Li6Cd5Sn4Se16Compound or according to mol ratio Li:Cd:Sn:Se=6:5:4:The mixing of 16 ratios Mixture is put into crystal growing apparatus, is warming up to melting sources, and after raw material is completely melt, crystal growing apparatus is with 0.1- 10mm/h speed vertically declines, and Li is carried out during crystal growing apparatus decline6Cd5Sn4Se16Nonlinear optical crystal is given birth to It is long, obtain Li6Cd5Sn4Se16Crystal；Its growth cycle is 5-20 days；
The powdered Li6Cd5Sn4Se16Preparing for compound is as follows:
By Li source materials, Cd source materials, Sn source materials and Se simple substance according to mol ratio Li:Cd:Sn:Se=6:5:4:16 Ratio it is well mixed after, be heated to 800-1050 DEG C of progress chemical synthesis, it is Li to obtain chemical formula6Cd5Sn4Se16Compound, Powdered Li is ground to obtain through smashing to pieces6Cd5Sn4Se16Compound；
The Li source materials are lithium simple substance or lithium selenide；
The Cd source materials are cadmium simple substance or cadmium selenide：
The Sn4Source material is tin simple substance or two stannic selenides.
The Li6Cd5Sn4Se16Prepared by following chemical equations：
(1) 6Li+5Cd+4Sn+16Se=Li6Cd5Sn4Se16；
(2)3Li2Se+5Cd+4Sn+13Se=Li6Cd5Sn4Se16；
(3) 6Li+5CdSe+4Sn+11Se=Li6Cd5Sn4Se16；
(4)6Li+5Cd+4SnSe2+ 8Se=Li6Cd5Sn4Se16；
(5)3Li2Se+5CdSe+4SnSe2=Li6Cd5Sn4Se16。
Above two method is used to obtain Li of the size for Centimeter Level6Cd5Sn4Se16Nonlinear optical crystal；Use Large scale crucible, and extend growth period, then it can obtain corresponding large-size Li6Cd5Sn4Se16Nonlinear optical crystal.
According to the crystallography data of crystal, crystal boule is oriented, cut by required angle, thickness and sectional dimension brilliant Body, by crystal thang-kng mirror polish, you can used as device for non-linear optical, the Li6Cd5Sn4Se16Nonlinear optical crystal has There is physical and chemical performance stable, hardness is larger, good mechanical property, not easily broken, and it is excellent to be not easy deliquescence, easy to process and preservation etc. Point；For this, the present invention furthermore provides Li6Cd5Sn4Se16The purposes of nonlinear optical crystal, the Li6Cd5Sn4Se16It is non-linear Optical crystal is used to prepare device for non-linear optical, and the device for non-linear optical, which includes, passes through at least a branch of incidence electromagnetic radiation At least one piece of Li6Cd5Sn4Se16The output that at least a branch of frequency is different from incidence electromagnetic radiation is produced after nonlinear optical crystal The device of radiation.
The Li of the present invention6Cd5Sn4Se16Compound, the compound nonlinear optical crystal and preparation method thereof and use Way has the effect that：
In the Li6Cd5Sn4Se16The growing crystals of nonlinear optical crystal are easily grown up and transparent no parcel, have growth Speed, cost is low, the advantages that being readily available large-size crystal；The Li obtained6Cd5Sn4Se16Nonlinear optical crystal With wider transmission region, hardness is larger, good mechanical property, not easily broken and deliquescence, it is easy to process and preserve the advantages that； The Li6Cd5Sn4Se16Nonlinear optical crystal can be used for making device for non-linear optical.
Brief description of the drawings
Fig. 1 is to use Li of the present invention6Cd5Sn4Se16A kind of typical nonlinear optics device made of nonlinear optical crystal The fundamental diagram of part, wherein 1 is laser, 2 be incoming laser beam, and 3 be after crystal post processing and optical manufacturing Li6Cd5Sn4Se16Nonlinear optical crystal, 4 be caused shoot laser beam, and 5 be filter plate.
Fig. 2 is Li6Cd5Sn4Se16The structural representation of nonlinear optical crystal.
Embodiment
Embodiment 1, Li is prepared using high-temperature fusant spontaneous crystallization method6Cd5Sn4Se16Crystal：
Weigh 2.785 grams of Li2Se, 9.568 grams of CdSe and 11.065 gram of SnSe2(i.e. Li2Se：CdSe：SnSe2= 0.03mol：0.05mol：0.04mol), uniformly it is fitted into Φ 12mm × 20mm quartz glass tube, is evacuated to after mixing 10-3After pa, it is placed in after being encapsulated with oxyhydrogen flame in tubular type growth furnace, rises to 900 DEG C, constant temperature 72 hours, delayed with 5 DEG C/h speed It is slow to be cooled to room temperature, close tubular type growth furnace；Cut after quartz ampoule cooling, can obtain transparent Li6Cd5Sn4Se16Crystal.
Embodiment 2, Li is prepared using Bridgman-Stockbarger method6Cd5Sn4Se16Crystal：
Weigh 0.417 gram of Li, 5.621 grams of Cd, 4.748 grams of Sn and 12.634 gram of Se (Li:Cd:Sn:Se=0.06mol: 0.05mol:0.04mol:0.16mol), uniformly it is fitted into Φ 20mm × 30mm quartz glass tube, is evacuated to after mixing 10-3After pa, it is placed in after being encapsulated with oxyhydrogen flame in crystal growing furnace, rising to 900 DEG C makes melting sources, after raw material is completely melt, Grower is vertically declined with the speed of 0.1-10mm/ hours；After crystal growth terminates, grower was down to room with 20 hours Temperature, obtain transparent Li6Cd5Sn4Se16Crystal.
After tested, the Li prepared by above-described embodiment 1-26Cd5Sn4Se16Nonlinear optical crystal category rhombic system, space Group is Pna21, its cell parameter is：α=β=γ=90 °, Z= 7,Density：5.453g/cm3, there is frequency-doubled effect；Fig. 2 is the Li6Cd5Sn4Se16Nonlinear optical crystal Structural representation.
Embodiment 3：
Li obtained by embodiment 1-26Cd5Sn4Se16Crystal is not easily broken, is easy to cutting, polishing and preservation, not damp Solution；By the Li obtained by embodiment 1-26Cd5Sn4Se16Crystal, opening position of the shown device of accompanying drawing 1 marked as 3 is placed on, in room temperature Under, with the Ho for adjusting Q:Tm:Cr:YAG laser makees light source, and incident wavelength is 2090nm infrared light, output wavelength 1045nm Frequency doubled light, laser intensity is and AgGaSe2Quite.
Accompanying drawing 1 is to use Li of the present invention6Cd5Sn4Se16A kind of typical nonlinear optics made of nonlinear optical crystal The fundamental diagram of device, wherein 1 is laser, 2 be incoming laser beam, and 3 be after crystal post processing and optical manufacturing Li6Cd5Sn4Se16Nonlinear optical crystal, 4 be caused shoot laser beam, and 5 be filter plate；Incidence is sent by laser 1 Laser beam 2 injects Li6Cd5Sn4Se16Monocrystal 3, caused shoot laser beam 4 is by filter plate 5, and swashing required for obtaining Light beam；
Use the Li of the present invention6Cd5Sn4Se16The device that nonlinear optical crystal makes can be a times frequency generator, upper and lower Frequency converter, optical parametric oscillator.Photoparametric amplifier etc..
It should be noted that the present invention can also directly use powdered Li6Cd5Sn4Se16The preparation of compound Li6Cd5Sn4Se16Monocrystal：Powdered Li6Cd5Sn4Se16The preparation of compound：By Li source materials, Cd source materials, Sn4Source material With Se simple substance according to mol ratio Li:Cd:Sn4:Se=7:4.5:4:After 16 ratio is well mixed, it is heated to 800-1050 DEG C and enters Row chemical synthesis, it is Li to obtain chemical formula6Cd5Sn4Se16Compound, grind to obtain powdered Li through smashing to pieces6Cd5Sn4Se16Chemical combination Thing；The preferred solid reaction process of chemical synthesis process of the present invention；The Li of the present invention6Cd5Sn4Se16Compound can be by following reactions It is prepared by formula：
(1) 6Li+5Cd+4Sn+16Se=Li6Cd5Sn4Se16；
(2)3Li2Se+5Cd+4Sn+13Se=Li6Cd5Sn4Se16；
(3) 6Li+5CdSe+4Sn+11Se=Li6Cd5Sn4Se16；
(4)6Li+5Cd+4SnSe2+ 8Se=Li6Cd5Sn4Se16；
(5)3Li2Se+5CdSe+4SnSe2=Li6Cd5Sn4Se16；
Above-mentioned powdered Li6Cd5Sn4Se16Li source materials in prepared by compound and its nonlinear chemical crystal can be lithium list Matter or lithium selenide；Cd source materials can be cadmium simple substance or cadmium selenide；Sn4Source material can be tin simple substance or two stannic selenides.

Claims (7)

  1. A kind of 1. Li6Cd5Sn4Se16Nonlinear optical crystal, the Li6Cd5Sn4Se16Nonlinear optical crystal do not possess have it is symmetrical in The heart, belong to rhombic system, space group Pna21, its cell parameter is： α=β =γ=90 °.
  2. A kind of 2. Li described in claim 16Cd5Sn4Se16The preparation method of nonlinear optical crystal, it is the spontaneous knot of high-temperature fusant Crystallization grows Li6Cd5Sn4Se16Nonlinear optical crystal, its step are：
    By Li6Cd5Sn4Se16Compound or according to mol ratio Li:Cd:Sn:Se=6:5:4:Li source materials, the Cd of 16 ratios mixing The mixture of source material, Sn source materials and Se simple substance is heated to melting to obtain high temperature solution, and keeps 24-96 small the high temperature solution When, afterwards, room temperature is cooled to 1-10 DEG C/h of rate of temperature fall, obtains Li6Cd5Sn4Se16Crystal；
    Powdered Li6Cd5Sn4Se16Preparing for compound is as follows：
    By Li source materials, Cd source materials, Sn source materials and Se simple substance according to mol ratio Li:Cd:Sn:Se=6:5:4:16 ratio After well mixed, 800-1050 DEG C of progress chemical synthesis is heated to, it is Li to obtain chemical formula6Cd5Sn4Se16Compound, through smashing to pieces Grind to obtain powdered Li6Cd5Sn4Se16Compound；
    The Li source materials are lithium simple substance or lithium selenide；
    The Cd source materials are cadmium simple substance or cadmium selenide；
    The Sn source materials are tin simple substance or two stannic selenides.
  3. 3. the Li as described in claim 26Cd5Sn4Se16The preparation method of nonlinear optical crystal, it is characterised in that described Chemical synthesis is solid phase reaction.
  4. 4. the Li as described in claim 26Cd5Sn4Se16The preparation method of nonlinear optical crystal, it is characterised in that powdered Li6Cd5Sn4Se16Compound is prepared according to the following reaction formula:
    (1) 6Li+5Cd+4Sn+16Se=Li6Cd5Sn4Se16；
    (2)3Li2Se+5Cd+4Sn+13Se=Li6Cd5Sn4Se16；
    (3) 6Li+5CdSe+4Sn+11Se=Li6Cd5Sn4Se16；
    (4)6Li+5Cd+4SnSe2+ 8Se=Li6Cd5Sn4Se16；
    (5)3Li2Se+5CdSe+4SnSe2=Li6Cd5Sn4Se16。
  5. A kind of 5. Li described in claim 16Cd5Sn4Se16The preparation method of nonlinear optical crystal, it is Bridgman-Stockbarge method for growing Li6Cd5Sn4Se16Nonlinear optical crystal, its step are as follows：
    By Li6Cd5Sn4Se16Compound or according to mol ratio Li:Cd:Sn:Se=6:5:4:The mixture of 16 ratios mixing is put into In crystal growing apparatus, melting sources are warming up to, after raw material is completely melt, crystal growing apparatus is with 0.1-10mm/h speed It is vertical to decline, carry out Li during crystal growing apparatus decline6Cd5Sn4Se16Nonlinear optical crystal grows, and obtains Li6Cd5Sn4Se16Nonlinear optical crystal；Its growth cycle is 5-20 days；
    Powdered Li6Cd5Sn4Se16Preparing for compound is as follows:
    By Li source materials, Cd source materials, Sn source materials and Se simple substance according to mol ratio Li:Cd:Sn:Se=6:5:4:16 ratio After well mixed, 800-1050 DEG C of progress chemical synthesis is heated to, it is Li to obtain chemical formula6Cd5Sn4Se16Compound, through smashing to pieces Grind to obtain powdered Li6Cd5Sn4Se16Compound；
    The Li source materials are lithium simple substance or lithium selenide；
    The Cd source materials are cadmium simple substance or cadmium selenide；
    The Sn source materials are tin simple substance or two stannic selenides.
  6. 6. the Li as described in claim 56Cd5Sn4Se16The preparation method of nonlinear optical crystal, it is characterised in that described Li6Cd5Sn4Se16Prepared by following chemical equations：
    (1) 6Li+5Cd+4Sn+16Se=Li6Cd5Sn4Se16；
    (2)3Li2Se+5Cd+4Sn+13Se=Li6Cd5Sn4Se16；
    (3) 6Li+5CdSe+4Sn+11Se=Li6Cd5Sn4Se16；
    (4)6Li+5Cd+4SnSe2+ 8Se=Li6Cd5Sn4Se16；
    (5)3Li2Se+5CdSe+4SnSe2=Li6Cd5Sn4Se16。
  7. A kind of 7. Li described in claim 16Cd5Sn4Se16The purposes of nonlinear optical crystal, it is characterised in that should Li6Cd5Sn4Se16Nonlinear optical crystal is used to prepare device for non-linear optical, and prepared device for non-linear optical includes will At least a branch of incidence electromagnetic radiation passes through at least one piece of Li6Cd5Sn4Se16At least a branch of frequency is produced after nonlinear optical crystal Different from the device of the output radiation of incidence electromagnetic radiation.
CN201511020624.0A 2015-12-29 2015-12-29 A kind of Li6Cd5Sn4Se16Nonlinear optical crystal and its preparation method and purposes Expired - Fee Related CN105506743B (en)

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CN109137079A (en) * 2017-09-18 2019-01-04 中国科学院理化技术研究所 A kind of Li2MnSnSe4Nonlinear optical crystal and its preparation method and application
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CN109161969A (en) * 2018-08-28 2019-01-08 中国科学院理化技术研究所 A kind of K2MnGe3S8Nonlinear optical crystal and preparation method and purposes
CN109610002A (en) * 2018-11-29 2019-04-12 中国科学院理化技术研究所 Inorganic compound, its purposes and preparation as non-linear optical crystal material
CN110284196B (en) * 2019-07-24 2020-07-31 中国科学院福建物质结构研究所 Lithium-containing crystal material and preparation method and application thereof

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CN101767778B (en) * 2010-02-03 2012-08-15 中国科学院理化技术研究所 BaCa4Se7 compound, BaCa4Se7 nonlinear optical crystal, preparation method and application
CN102094245A (en) * 2010-12-08 2011-06-15 中国科学院理化技术研究所 Selenium-gallium-aluminum-barium compound, selenium-gallium-aluminum-barium nonlinear optical crystal and preparation methods and applications of compound and nonlinear optical crystal
CN103058266A (en) * 2011-10-20 2013-04-24 中国科学院理化技术研究所 BaGa2GeS6 compound, BaGa2GeS6 nonlinear optical crystal, and preparation method and application thereof
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