CN108385165A - A kind of second-order non-linear optical materials, preparation method and application - Google Patents
A kind of second-order non-linear optical materials, preparation method and application Download PDFInfo
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- CN108385165A CN108385165A CN201810338698.6A CN201810338698A CN108385165A CN 108385165 A CN108385165 A CN 108385165A CN 201810338698 A CN201810338698 A CN 201810338698A CN 108385165 A CN108385165 A CN 108385165A
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- 239000000463 material Substances 0.000 title claims abstract description 94
- 230000003287 optical effect Effects 0.000 title claims abstract description 71
- 238000002360 preparation method Methods 0.000 title description 15
- 239000000126 substance Substances 0.000 claims abstract description 44
- 229910052783 alkali metal Inorganic materials 0.000 claims abstract description 5
- 150000001340 alkali metals Chemical class 0.000 claims abstract description 5
- 229910052736 halogen Inorganic materials 0.000 claims abstract description 5
- 150000002367 halogens Chemical class 0.000 claims abstract description 5
- 239000002994 raw material Substances 0.000 claims description 52
- 239000000203 mixture Substances 0.000 claims description 49
- 229910052733 gallium Inorganic materials 0.000 claims description 47
- 229910052788 barium Inorganic materials 0.000 claims description 46
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 claims description 46
- GYHNNYVSQQEPJS-UHFFFAOYSA-N Gallium Chemical compound [Ga] GYHNNYVSQQEPJS-UHFFFAOYSA-N 0.000 claims description 39
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 30
- 238000010438 heat treatment Methods 0.000 claims description 30
- 229910052717 sulfur Inorganic materials 0.000 claims description 30
- 239000011593 sulfur Substances 0.000 claims description 28
- 238000002156 mixing Methods 0.000 claims description 23
- 238000000034 method Methods 0.000 claims description 15
- -1 barium sulfide compound Chemical class 0.000 claims description 14
- 238000006243 chemical reaction Methods 0.000 claims description 12
- 150000004820 halides Chemical class 0.000 claims description 10
- 229910052794 bromium Inorganic materials 0.000 claims description 8
- 229910052792 caesium Inorganic materials 0.000 claims description 8
- 229910052801 chlorine Inorganic materials 0.000 claims description 8
- 229910052731 fluorine Inorganic materials 0.000 claims description 8
- 229910052740 iodine Inorganic materials 0.000 claims description 8
- 229910052700 potassium Inorganic materials 0.000 claims description 8
- 229910052701 rubidium Inorganic materials 0.000 claims description 8
- 229910052708 sodium Inorganic materials 0.000 claims description 8
- RKTYLMNFRDHKIL-UHFFFAOYSA-N copper;5,10,15,20-tetraphenylporphyrin-22,24-diide Chemical compound [Cu+2].C1=CC(C(=C2C=CC([N-]2)=C(C=2C=CC=CC=2)C=2C=CC(N=2)=C(C=2C=CC=CC=2)C2=CC=C3[N-]2)C=2C=CC=CC=2)=NC1=C3C1=CC=CC=C1 RKTYLMNFRDHKIL-UHFFFAOYSA-N 0.000 claims description 5
- 239000007795 chemical reaction product Substances 0.000 claims 1
- 239000002178 crystalline material Substances 0.000 claims 1
- 230000005855 radiation Effects 0.000 abstract description 3
- 238000002834 transmittance Methods 0.000 abstract description 2
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 abstract 1
- 239000013078 crystal Substances 0.000 description 48
- 238000001816 cooling Methods 0.000 description 31
- FGDZQCVHDSGLHJ-UHFFFAOYSA-M rubidium chloride Chemical compound [Cl-].[Rb+] FGDZQCVHDSGLHJ-UHFFFAOYSA-M 0.000 description 20
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 description 18
- 230000004907 flux Effects 0.000 description 18
- 239000010453 quartz Substances 0.000 description 13
- 238000007789 sealing Methods 0.000 description 13
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 13
- AIYUHDOJVYHVIT-UHFFFAOYSA-M caesium chloride Chemical compound [Cl-].[Cs+] AIYUHDOJVYHVIT-UHFFFAOYSA-M 0.000 description 12
- 239000000843 powder Substances 0.000 description 11
- 239000001103 potassium chloride Substances 0.000 description 9
- 235000011164 potassium chloride Nutrition 0.000 description 9
- NLKNQRATVPKPDG-UHFFFAOYSA-M potassium iodide Chemical compound [K+].[I-] NLKNQRATVPKPDG-UHFFFAOYSA-M 0.000 description 9
- FVAUCKIRQBBSSJ-UHFFFAOYSA-M sodium iodide Chemical compound [Na+].[I-] FVAUCKIRQBBSSJ-UHFFFAOYSA-M 0.000 description 9
- 229910001508 alkali metal halide Inorganic materials 0.000 description 7
- 150000008045 alkali metal halides Chemical class 0.000 description 7
- 229910001615 alkaline earth metal halide Inorganic materials 0.000 description 7
- 239000011734 sodium Substances 0.000 description 7
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 6
- WDIHJSXYQDMJHN-UHFFFAOYSA-L barium chloride Chemical compound [Cl-].[Cl-].[Ba+2] WDIHJSXYQDMJHN-UHFFFAOYSA-L 0.000 description 6
- 229910001626 barium chloride Inorganic materials 0.000 description 6
- IOLCXVTUBQKXJR-UHFFFAOYSA-M potassium bromide Chemical compound [K+].[Br-] IOLCXVTUBQKXJR-UHFFFAOYSA-M 0.000 description 6
- JAAGVIUFBAHDMA-UHFFFAOYSA-M rubidium bromide Chemical compound [Br-].[Rb+] JAAGVIUFBAHDMA-UHFFFAOYSA-M 0.000 description 6
- 229940102127 rubidium chloride Drugs 0.000 description 6
- WFUBYPSJBBQSOU-UHFFFAOYSA-M rubidium iodide Chemical compound [Rb+].[I-] WFUBYPSJBBQSOU-UHFFFAOYSA-M 0.000 description 6
- JHJLBTNAGRQEKS-UHFFFAOYSA-M sodium bromide Chemical compound [Na+].[Br-] JHJLBTNAGRQEKS-UHFFFAOYSA-M 0.000 description 6
- 238000001228 spectrum Methods 0.000 description 6
- 239000003795 chemical substances by application Substances 0.000 description 4
- 239000013307 optical fiber Substances 0.000 description 4
- 239000002245 particle Substances 0.000 description 4
- 238000004321 preservation Methods 0.000 description 4
- LYQFWZFBNBDLEO-UHFFFAOYSA-M caesium bromide Chemical compound [Br-].[Cs+] LYQFWZFBNBDLEO-UHFFFAOYSA-M 0.000 description 3
- XQPRBTXUXXVTKB-UHFFFAOYSA-M caesium iodide Chemical compound [I-].[Cs+] XQPRBTXUXXVTKB-UHFFFAOYSA-M 0.000 description 3
- 238000011161 development Methods 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- 238000002474 experimental method Methods 0.000 description 3
- 238000011049 filling Methods 0.000 description 3
- 239000011780 sodium chloride Substances 0.000 description 3
- 235000009518 sodium iodide Nutrition 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 238000004458 analytical method Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000011534 incubation Methods 0.000 description 2
- 238000011068 loading method Methods 0.000 description 2
- 230000010355 oscillation Effects 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 238000012216 screening Methods 0.000 description 2
- 229910013321 LiB3O5 Inorganic materials 0.000 description 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- 229910007475 ZnGeP2 Inorganic materials 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
- 125000000129 anionic group Chemical group 0.000 description 1
- NKQIMNKPSDEDMO-UHFFFAOYSA-L barium bromide Chemical compound [Br-].[Br-].[Ba+2] NKQIMNKPSDEDMO-UHFFFAOYSA-L 0.000 description 1
- 229910001620 barium bromide Inorganic materials 0.000 description 1
- SGUXGJPBTNFBAD-UHFFFAOYSA-L barium iodide Chemical compound [I-].[I-].[Ba+2] SGUXGJPBTNFBAD-UHFFFAOYSA-L 0.000 description 1
- 229910001638 barium iodide Inorganic materials 0.000 description 1
- 229940075444 barium iodide Drugs 0.000 description 1
- CJDPJFRMHVXWPT-UHFFFAOYSA-N barium sulfide Chemical compound [S-2].[Ba+2] CJDPJFRMHVXWPT-UHFFFAOYSA-N 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 238000004891 communication Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 230000009022 nonlinear effect Effects 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 238000000634 powder X-ray diffraction Methods 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 238000004088 simulation Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
Classifications
-
- 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
-
- 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
- C30B1/00—Single-crystal growth directly from the solid state
- C30B1/10—Single-crystal growth directly from the solid state by solid state reactions or multi-phase diffusion
-
- 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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- Chemical & Material Sciences (AREA)
- Physics & Mathematics (AREA)
- Crystallography & Structural Chemistry (AREA)
- Nonlinear Science (AREA)
- Metallurgy (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Optics & Photonics (AREA)
- Inorganic Chemistry (AREA)
- General Physics & Mathematics (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Crystals, And After-Treatments Of Crystals (AREA)
Abstract
This application discloses a kind of second-order non-linear optical materials, which is characterized in that has chemical formula：ABaxX1+2x‑mGamS2m；Wherein, A is selected from least one of alkali metal, and X is selected from least one of halogen；X is 1,2 or 3；M is any positive integer in 1,2,3,4 or 5；The second-order non-linear optical materials meet phase matched at least one wavelength of infrared band.The Clock Multiplier Factor of the material is commercial AgGaS20.5~10 times, laser damage threshold is commercial AgGaS21~50 times, performance improves a lot, and is potential FTIR radiation transmittance.
Description
Technical Field
The application relates to a second-order nonlinear optical material, a preparation method and application thereof, belonging to the field of nonlinear optical materials.
Background
The second-order nonlinear optical material has important application in the field of electrooptical device in frequency-doubling conversion effect, such as frequency doubling, difference frequency, sum frequency, optical parametric oscillation, etc. In recent years, with CO2The rapid development of laser radar detection, laser communication, infrared remote measurement, infrared navigation and other technologies has more and more urgent requirements on high-quality and high-performance infrared nonlinear optical materials. The ideal nonlinear material should have the following properties: (1) the nonlinear effect is large, (2) the transmission range is wide, (3) the laser damage threshold is high, (4) phase matching is met, and (5) the mechanical, chemical and thermal stability is good. After many years of research and study in the field of nonlinear optical crystals, second-order nonlinear oxide materials such as KH are currently used2PO4，KTiOPO4，β-BaB2O4，LiB3O5And the like, basically meets the requirements of the development of the laser from ultraviolet to visible light,a huge industrial chain is formed. However, the main NLO material applied in the middle and far infrared band is AgGaS2，AgGaSe2And ZnGeP2The materials have large nonlinear coefficient and high transmittance in middle and far infrared bands, but have low laser damage threshold value, and cannot meet the development requirement of high-power laser. Therefore, the search for synthesizing nonlinear materials having both a large nonlinear coefficient and a high laser damage threshold has become an important research direction for infrared nonlinear materials.
Disclosure of Invention
According to one aspect of the present application, a second order nonlinear optical material is provided. The frequency multiplication coefficient of the material is commercial AgGaS20.5-10 times of the laser damage threshold value of the commercial AgGaS21-50 times of the total amount of the optical fiber, the performance is greatly improved, and the optical fiber is a potential infrared nonlinear optical material.
The second-order nonlinear optical material has a chemical formula shown as a formula I:
ABaxX1+2x-mGamS2mformula I;
wherein A is at least one of alkali metals, and X is at least one of halogen elements;
x is selected from 1, 2 or 3; m is selected from any positive integer of 1, 2, 3, 4 or 5;
the second-order nonlinear optical material satisfies phase matching at least one wavelength of an infrared band.
Optionally, the second-order nonlinear optical material has a chemical formula shown in formula I':
[ABaxX1+2x-m][GamS2m]formula I';
wherein A is at least one of alkali metals, and X is at least one of halogen elements;
x is selected from 1, 2 or 3; m is selected from any positive integer of 1, 2, 3, 4 or 5;
the second-order nonlinear optical material satisfies phase matching at least one wavelength of an infrared band.
Optionally, the second-order nonlinear optical material includes a T2 super-tetrahedron structure and four GaS groups formed by Ga and S4The tetrahedra are joined by a common point S to form a structure having four Ga-S six-membered rings.
Optionally, A is selected from at least one of Na, K, Rb and Cs; x is at least one of F, Cl, Br and I.
Optionally, the second order nonlinear optical material satisfies phase matching at least one wavelength in the near infrared band.
Optionally, the second order nonlinear optical material is type I phase matched at 1910 nm.
Optionally, the material belongs to the tetragonal I-4 space group, orthorhombic Pmn21Space group or a Pm space group of monoclinic system, and the unit cell parameters are as follows: and Z is 1 or 2.
Optionally, the second-order nonlinear optical material is one of a material with a chemical formula of formula II and a crystal material with a chemical formula of formula III;
[ABa3X2][Ga5S10]formula II;
a material of formula II belonging to the tetragonal system, space group I-4, having a unit cell parameter of b＝8.34～8.52，α＝90°，β＝90°，γ＝90°，Z＝2；
[ABa2X][Ga4S8]Formula III;
a material of formula III belonging to the orthorhombic system, space group Pmn21，b＝6.24～6.75，α＝90°，β＝90°，γ＝90°， Z＝2；
Or,
the material with the chemical formula of formula III belongs to a monoclinic system, a space group Pm,b＝6.55～7.97，α＝90°，β＝107.1～109.2°，γ＝90°，Z＝1。
optionally, the second-order nonlinear optical material has a chemical formula [ ABa3Cl2][Ga5S10]；
The crystal structure of the second-order nonlinear optical material belongs to a tetragonal system, a space group I-4 and unit cell parameters ofb＝8.3438(1)～8.5177(5)， α＝90°，β＝90°，γ＝90°， Z＝2。
Optionally, the second-order nonlinear optical material has a chemical formula [ ABa2Cl][Ga4S8]；
The crystal structure of the second-order nonlinear optical material belongs to an orthorhombic system, and the space group Pmn21，b＝6.2440(1)～6.7440(5)， α＝90°，β＝90°，γ＝90°，Z＝2。
Optionally, the second-order nonlinear optical material has a chemical formula [ ABa2Cl][Ga4S8]；
The second orderThe crystal structure of the nonlinear optical material belongs to a monoclinic system, a space group Pm, b＝6.5514(1)～7.9612,α＝90°，β＝107.1～109.2°，γ＝90°，Z＝1。
according to still another aspect of the present application, there is provided a method of preparing the second-order nonlinear optical material, comprising at least:
and heating a mixture containing barium element, gallium element, sulfur element, A element and X element to a reaction temperature under a vacuum condition, and reacting to obtain the second-order nonlinear optical material.
Alternatively, the following molar ratios are satisfied in the mixture:
Ba：Ga：S＝1～11：3～10：4～16。
alternatively, the following molar ratios are satisfied in the mixture:
Ba：Ga：S：A：X＝1～11：3～10：4～16：1～20：1～20。
optionally, the mixture comprises barium raw material, gallium raw material, sulfur raw material and AX in a molar ratio satisfying:
Ba：Ga：S：AX＝1：3：4～16：1～20。
alternatively, the AX is a flux, and can be added by those skilled in the art according to actual needs.
Alternatively, the following molar ratios are satisfied in the mixture:
Ba：Ga：S：A：X＝1：4：4～16：1～20：1～20。
alternatively, the following molar ratios are satisfied in the mixture:
Ba：Ga：S：A：X＝2～11：10：4～16：1～20：1～40。
optionally, the mixture comprises barium raw material, gallium raw material, sulfur raw material and AX in a molar ratio satisfying:
Ba：Ga：S：AX＝1：4：4～16：1～20。
alternatively, the following molar ratios are satisfied in the mixture:
Ba：Ga：S＝1～11：3～4：4～10。
alternatively, the following molar ratios are satisfied in the mixture:
Ba：Ga：S：A：X＝1～11：3～4：4～10：1～20：1～20。
alternatively, the following molar ratios are satisfied in the mixture:
Ba：Ga：S：A：X＝1：4：4～10：1～20：1～20。
optionally, the mixture comprises barium raw material, gallium raw material, sulfur raw material and AX in a molar ratio satisfying:
Ba：Ga：S：AX＝1：4：4～10：1～20。
optionally, the mixture comprises barium raw material, gallium raw material, sulfur raw material and AX in a molar ratio satisfying:
Ba：Ga：S：AX＝1：3：4～10：1～20。
optionally, the mixture comprises barium raw material, gallium raw material, sulfur raw material and AX in a molar ratio satisfying:
Ba：Ga：S：AX＝1：5：9：1～20。
optionally, the mixture comprises barium raw material, gallium raw material, sulfur raw material and AX in a molar ratio satisfying:
Ba：Ga：S：AX＝1：4：9：1～20。
optionally, the mixture comprises barium raw material, gallium raw material, sulfur raw material and AX in a molar ratio satisfying:
Ba：Ga：S：AX＝1：3：7：1～20。
optionally, the mixture comprises barium raw material, gallium raw material, sulfur raw material and AX in a molar ratio satisfying:
Ba：Ga：S：AX＝1：3：5：1～20。
optionally, the mixture comprises barium raw material, gallium raw material, sulfur raw material and AX in a molar ratio satisfying:
Ba：Ga：S：AX＝1：3.6：6.4：1～20。
optionally, the mixture comprises barium raw material, gallium raw material, sulfur raw material and AX in a molar ratio satisfying:
Ba：Ga：S：AX＝1：10：7：1～20。
alternatively, the AX is a flux, and can be added by those skilled in the art according to actual needs.
Alternatively, the following molar ratios are satisfied in the mixture:
Ba：Ga：S：A：X＝2～11：4：4～10：5～20：7～40。
optionally, the mixture includes barium raw material, gallium raw material, sulfur raw material, AX and BaX2The molar ratio satisfies:
Ba：Ga：S：AX：BaX2＝1：4：4～10：5～20：1～10；
wherein the mole number of Ba is the mole number of Ba in the raw material of Ba, excluding BaX2Mole number of Ba in the compound (B).
Optionally, the AX and BaX2A flux, and those skilled in the art can add the flux according to actual needs.
Optionally, the source of Ba in the mixture is selected from at least one of simple substance of barium, barium sulfide compound, and halide of barium.
Optionally, the source of Ga in the mixture is selected from at least one of elemental gallium and gallium sulfide compounds.
Optionally, the source of S in the mixture is selected from at least one of barium sulfide compound, gallium sulfide compound, and sulfur powder.
Optionally, the source of a in the mixture is selected from at least one of the halides of a.
Optionally, the source of X in the mixture is selected from at least one of halides of a, halides of barium.
Optionally, a in the mixture and/or X in the mixture act as a fluxing agent.
Optionally, the flux is selected from at least one of sodium chloride, potassium chloride, rubidium chloride, cesium chloride, sodium bromide, potassium bromide, rubidium bromide, cesium bromide, sodium iodide, potassium iodide, rubidium iodide, and cesium iodide.
Optionally, the flux is selected from at least one of potassium chloride, rubidium chloride and cesium chloride.
Optionally, the flux is selected from at least one halide of a and at least one halide of Ba.
Optionally, the vacuum condition is 1Pa to 10 Pa-4Pa。
Optionally, theVacuum condition is 10-3Pa～10-4Pa。
Optionally, the reaction condition is heating to 600-1100 ℃ and preserving heat, and the heat preservation time is not less than 1 hour.
Optionally, the reaction condition is heating to 600-1100 ℃, preserving heat for not less than 1 hour, and then cooling.
Optionally, the upper limit of the heating temperature is selected from 800 ℃, 850 ℃, 900 ℃, 950 ℃, 1000 ℃ or 1100 ℃; the lower limit is selected from 600 deg.C, 650 deg.C, 700 deg.C or 800 deg.C. Optionally, the heat preservation time is 1-100 hours. The upper limit of the incubation time is selected from 72 hours, 86 hours, 90 hours or 100 hours; the lower limit is selected from 1 hour, 12 hours, 24 hours, 48 hours, 60 hours, or 72 hours.
Alternatively, the reaction mixture is cooled naturally after the reaction.
Optionally, after the reaction is finished, cooling to 100-500 ℃ at 1-10 ℃/h, and then naturally cooling.
Optionally, after the reaction is finished, cooling to 100-500 ℃ at 1-10 ℃/h, and then slowly cooling to room temperature. Optionally, after the reaction is finished, cooling to 350-450 ℃ at a speed of 4-6 ℃/h, and then naturally cooling.
Optionally, the particle size of the material prepared by the method is 1-300 nm.
Optionally, the particle size prepared by the method is any one range of 30-50 nm, 50-75 nm, 75-100 nm, 100-150 nm and 150-200 nm.
As a specific implementation mode, the raw material containing barium element, gallium element and sulfur element is mixed with fluxing agent uniformly, heated under vacuum condition, kept warm and then cooled to room temperature, and the nonlinear optical crystal material is prepared.
Optionally, the raw material containing barium element is selected from barium simple substance and/or barium sulfide.
Optionally, the gallium-containing feedstock is selected from elemental gallium and/or gallium sulfide.
Optionally, the raw material contains a simple substance of barium, a simple substance of gallium, and a simple substance of sulfur.
Optionally, the molar ratio of the barium element, the gallium element and the sulfur element in the raw material is Ba, Ga and S is 1:3: 4-10.
Optionally, the vacuum condition is that the pressure is 1-10-4Pa。
Optionally, the vacuum condition is a pressure of 10-3～10-4Pa。
Optionally, the heating temperature is 600-1100 ℃; the heat preservation time is not less than 1 hour.
Optionally, the upper limit of the heating temperature is selected from 800 ℃, 850 ℃, 900 ℃, 950 ℃, 1000 ℃ or 1100 ℃; the lower limit is selected from 600 deg.C, 650 deg.C, 700 deg.C or 800 deg.C.
Optionally, the heat preservation time is 1-100 hours. The upper limit of the incubation time is selected from 72 hours, 86 hours, 90 hours or 100 hours; the lower limit is selected from 1 hour, 12 hours, 24 hours, 48 hours, 60 hours, or 72 hours.
Optionally, the cooling is natural cooling.
Optionally, the temperature is reduced to 100-500 ℃ at a speed of 1-10 ℃/h, and then the product is naturally cooled.
Optionally, the flux is selected from at least one of alkali metal halides and alkaline earth metal halides.
Optionally, the molar ratio of the barium element to the flux is Ba: the flux is 1: 1-20.
Optionally, the molar ratio of the barium element to the flux is Ba: the flux is 1: 5-20.
Optionally, the flux is selected from at least one of sodium chloride, potassium chloride, rubidium chloride, cesium chloride, sodium bromide, potassium bromide, rubidium bromide, cesium bromide, sodium iodide, potassium iodide, rubidium iodide, and cesium iodide.
Optionally, the flux is selected from at least one of potassium chloride, rubidium chloride and cesium chloride.
Optionally, the fluxing agent contains at least one alkali metal halide and at least one alkaline earth metal halide.
Optionally, the molar ratio of the barium element, the alkali metal halide and the alkaline earth metal halide is Ba: alkali metal halides: an alkaline earth metal halide is 1:1 to 20:1 to 10.
Optionally, the molar ratio of the barium element, the alkali metal halide and the alkaline earth metal halide is Ba: alkali metal halides: the alkaline earth metal halide is 1:5 to 20:1 to 10.
Optionally, the alkali metal halide is selected from at least one of sodium chloride, potassium chloride, rubidium chloride, cesium chloride, sodium bromide, potassium bromide, rubidium bromide, cesium bromide, sodium iodide, potassium iodide, rubidium iodide, and cesium iodide.
Optionally, the flux is selected from potassium chloride, rubidium chloride, cesium chloride.
Optionally, the alkaline earth metal halide is selected from at least one of barium chloride, barium bromide, and barium iodide.
Optionally, the flux is selected from barium chloride.
The person skilled in the art can select the appropriate fluxing agent and the amount thereof according to the actual needs. The flux is preferably selected according to the flux and the amount thereof.
As an embodiment, the method comprises at least:
raw materials containing barium, gallium, sulfur and AX are mixed according to a molar ratio of Ba: ga: s: AX is 1:3: (4-16): (1-20) and uniformly mixing, and then mixing in a vacuum degree of 1Pa &10-4Heating to 600-1100 ℃ under the condition of Pa, and preserving heat for not less than 1 hour to obtain the second-order nonlinear optical material; the chemical formula is [ ABa3X2][Ga5S10](ii) a Or
Raw materials containing barium, gallium, sulfur and AX (are mixed according to the molar ratio of Ba to Ga to S to AX being 1 to 4 (4-16) to (1-20) and are uniformly mixed, and then the mixture is vacuumized to 1 Pa-10 Pa-4Heating to 600-1100 ℃ under the condition of Pa, and preserving heat for not less than 1 hour to obtain the second-order nonlinear optical material; the chemical formula is [ ABa2X][Ga4S8](ii) a Or
Raw materials containing barium, gallium, sulfur and AX are mixed according to a molar ratio of Ba: ga: s: AX: BaX21: 4: (4-16): (1-20): (1-10) mixing the materials according to the proportion, uniformly mixing, and keeping the vacuum degree at 1 Pa-10-4Heating to 600-1100 ℃ under the condition of Pa, and preserving heat for not less than 1 hour to obtain the second-order nonlinear optical material; the chemical formula is [ ABa2X][Ga4S8]。
Optionally, the method comprises at least:
raw materials containing barium, gallium, sulfur and AX are mixed according to a molar ratio of Ba: ga: s: AX is 1:3: (4-10): (5-20) mixing and uniformly mixing the materials in the ratio, and then keeping the vacuum degree at 10-3Pa～10-4Heating to 600-1100 ℃ under the condition of Pa, and preserving heat for not less than 1 hour to obtain the second-order nonlinear optical material; the chemical formula is [ ABa3X2][Ga5S10](ii) a Or
Raw materials containing barium, gallium, sulfur and AX (are mixed according to the molar ratio of Ba to Ga to S to AX being 1 to 4 (4-10) to (5-20) and are uniformly mixed, and then the mixture is vacuumized to 10 degrees-3Pa～10-4Heating to 600-1100 ℃ under the condition of Pa, and preserving the heat for not less than 1 hour to obtain the second-order nonlinear optical material; the chemical formula is [ ABa2X][Ga4S8](ii) a Or
Will containRaw materials with barium, gallium, sulfur and AX in molar ratio Ba: ga: s: AX: BaX21: 4: (4-10): (5-20): (1-10) mixing and uniformly mixing the materials in the ratio, and then keeping the vacuum degree at 10-3Pa～10-4Heating to 600-1100 ℃ under the condition of Pa, and preserving heat for not less than 1 hour to obtain the second-order nonlinear optical material; the chemical formula is [ ABa2X][Ga4S8]。
In one embodiment, barium, gallium, sulfur and AX (a ═ Na, K, Rb, Cs; X ═ F, Cl, Br, I) are mixed in a molar ratio of Ba: ga: s: AX is 1:3: (4-10): (5-20) mixing and uniformly mixing, filling into a quartz tube, and vacuumizing to 10 DEG-3Pa sealing the tube, putting the tube into a muffle furnace, slowly heating the tube to 600-1100 ℃, preserving the heat for not less than 1 hour, then closing the muffle furnace, and naturally cooling the tube to room temperature to obtain the chemical formula [ ABa ]3X2][Ga5S10](A ═ Na, K, Rb, Cs; X ═ F, Cl, Br, I). The raw material of the barium can be a barium simple substance or a barium sulfide compound; the raw material of gallium may be elemental gallium or a gallium sulfide compound.
In one embodiment, barium, gallium, sulfur and AX (a ═ Na, K, Rb, Cs; X ═ F, Cl, Br, I) are mixed in a molar ratio of Ba: ga: s: AX is 1: 4: (4-10): (5-20) mixing and uniformly mixing, filling into a quartz tube, and vacuumizing to 10 DEG-3Pa sealing the tube, putting the tube into a muffle furnace, slowly heating the tube to 600-1100 ℃, preserving the heat for not less than 1 hour, then closing the muffle furnace, and naturally cooling the tube to room temperature to obtain the chemical formula [ ABa ]2X][Ga4S8](A ═ Na, K, Rb, Cs; X ═ F, Cl, Br, I). The raw material of the barium can be a barium simple substance or a barium sulfide compound; the raw material of gallium may be elemental gallium or a gallium sulfide compound.
In one embodiment, barium, gallium, sulfur and AX (a ═ Na, K, Rb, Cs; X ═ F, Cl, Br, I) are mixed in a molar ratio of Ba: ga: s: AX: BaX21: 4: (4-10): (5-20): (1-10) mixing and uniformly mixing, then filling into a quartz tube, and vacuumizing to 10 DEG-3Pa sealing the tube, putting the tube into a muffle furnace, slowly heating the tube to 600-1100 ℃, preserving the heat for not less than 1 hour, then closing the muffle furnace, and naturally cooling the tube to room temperature to obtain the chemical formula [ ABa ]2X][Ga4S8](A ═ Na, K, Rb, Cs; X ═ F, Cl, Br, I). The raw material of the barium can be a barium simple substance or a barium sulfide compound; the raw material of gallium may be elemental gallium or a gallium sulfide compound.
According to a further aspect of the present application, there is provided a use of any of the above second order nonlinear optical materials and/or second order nonlinear optical materials prepared according to any of the above methods in a laser.
According to still another aspect of the present application, there is provided an infrared nonlinear optical material, comprising the second-order nonlinear optical material and/or the second-order nonlinear optical material prepared according to the above method.
Benefits that can be produced by the present application include, but are not limited to:
(1) the application provides a novel second-order nonlinear optical material. The frequency multiplication coefficient of the material is commercial AgGaS20.5-10 times of the laser damage threshold value of the commercial AgGaS21-50 times of the total amount of the optical fiber, the performance is greatly improved, and the optical fiber is a potential infrared nonlinear optical material.
(2) The application provides a preparation method of the second-order nonlinear optical material. The method has simple steps, and the obtained crystal material has high purity, good crystallinity and high yield, and is suitable for large-scale industrial production.
(3) The second-order nonlinear optical material provided by the application is a polar crystal with excellent infrared nonlinear optical effect, and the crystal has a larger frequency multiplication coefficient which is about AgGaS20.9 times of that of the formula I, and is in type I phase matching at 1910 nm. The method is expected to have important application value in the aspects of frequency conversion devices such as medium and far infrared band laser frequency doubling, sum frequency, difference frequency, optical parametric oscillation and the like.
Drawings
FIG. 1 shows sample 1#GaS obtained by fitting single crystal data4A super tetrahedral structure.
FIG. 2 shows sample 1#Powder diffraction pattern of (2).
FIG. 3 shows sample 2#Powder diffraction pattern of (2).
FIG. 4 shows sample 5#Powder diffraction pattern of (2).
FIG. 5 shows the doubling intensity as a function of sample 1#Sample 2#Sample No. 5#And AgGaS2Variation curve of powder particle size.
FIG. 6 shows sample 1#The crystal structure of (1).
FIG. 7 shows sample 4#The crystal structure of (1).
FIG. 8 shows sample 7#The crystal structure of (1).
Detailed Description
The present invention will be described in more detail with reference to examples, but the present invention is not limited to these examples.
Example 1 sample 1#Preparation of
Mixing Ba (68mg), Ga (104mg), S (80mg) and KCl (150mg) uniformly, loading into quartz tube, and vacuumizing to 10%-4Pa sealing the tube, placing the tube in a muffle furnace, slowly heating to 950 ℃, preserving heat for 72 hours, cooling to 400 ℃ at a speed of 5 ℃/h, closing the muffle furnace, and naturally cooling to room temperature to obtain the chemical formula of [ KBa ]3Cl2][Ga5S10](space group: I-4). The obtained crystal was designated as sample 1#。
Example 2 sample 2#Preparation of
Ba (68mg), Ga (104mg), S (80mg) and RbCl (150mg) are mixed and mixed evenly, then the mixture is put into a quartz tube and vacuumized to 10 degrees-4Pa sealing the tube, placing the tube in a muffle furnace, slowly heating to 950 ℃, keeping the temperature for 72 hours, then closing the muffle furnace, and naturally cooling to room temperature to obtain the chemical formula [ RbBa3Cl2][Ga5S10](space group: I-4). The obtained crystal was designated as sample 2#。
Example 3 sample 3#Preparation of
Ba (53mg), Ga (135mg), S (112mg) and RbCl (150mg) were mixed and mixed uniformly, and then the mixture was put into a quartz tube and evacuated to 10 degrees centigrade-4Pa sealing the tube, placing the tube in a muffle furnace, slowly heating to 950 ℃, preserving heat for 72 hours, cooling to 400 ℃ at the rate of 5 ℃/h, closing the muffle furnace, and naturally cooling to room temperature to obtain the chemical formula [ RbBa2Cl][Ga4S8](space group: Pmn21) The crystal of (4). The obtained crystal was designated as sample 3#。
Example 4 sample 4#Preparation of
Ba (70mg), Ga (127mg), S (104mg), CsCl (150mg), BaCl2(100mg) are mixed and evenly mixed, then the mixture is put into a quartz tube and vacuumized to 10 degrees-4Pa sealing the tube, placing the tube in a muffle furnace, slowly heating to 900 ℃, preserving heat for 72 hours, cooling to 400 ℃ at the rate of 5 ℃/h, closing the muffle furnace, and naturally cooling to room temperature to obtain the chemical formula [ CsBa ]2Cl][Ga4S8](space group: Pm). The obtained sample was named 4#。
Example 5 sample 5#Preparation of
The mixture of Ba (77mg),ga (115mg), S (123mg) and CsCl (185mg) were compounded and mixed well, and then charged into a quartz tube and evacuated to 10 degrees-4Pa sealing the tube, placing the tube in a muffle furnace, slowly heating to 950 ℃, preserving heat for 72 hours, cooling to 400 ℃ at the rate of 5 ℃/h, closing the muffle furnace, and naturally cooling to room temperature to obtain the chemical formula [ CsBa ]3Cl2][Ga5S10](space group: I-4). The obtained crystal was designated as sample 5#。
Example 6 sample 6#Preparation of
Ba (75mg), Ga (189mg), S (156mg) and KCl (322mg) are mixed and mixed evenly, then the mixture is put into a quartz tube and vacuumized to 10 degrees-4Pa sealing the tube, placing the tube in a muffle furnace, slowly heating to 950 ℃, preserving heat for 72 hours, cooling to 400 ℃ at a speed of 5 ℃/h, closing the muffle furnace, and naturally cooling to room temperature to obtain the chemical formula of [ KBa ]2Cl][Ga4S8](space group: Pmn21) The crystal of (4). The obtained crystal was designated as sample 6#。
Example 7 sample 7#Preparation of
Ba (66mg), Ga (133mg), S (139mg) and CsCl (321mg) were charged and mixed uniformly, and then the mixture was charged into a quartz tube and evacuated to 10 deg.C-4Pa sealing the tube, placing the tube in a muffle furnace, slowly heating to 950 ℃, preserving heat for 72 hours, cooling to 400 ℃ at the rate of 5 ℃/h, closing the muffle furnace, and naturally cooling to room temperature to obtain the chemical formula [ CsBa ]2Cl][Ga4S8](space group: Pmn21) The crystal of (4). The resulting crystal was designated as sample 7#。
Example 8 sample 8#Preparation of
Ba (88mg), Ga (179mg), S (185mg), KCl (50mg) BaCl2(85mg) and after being mixed evenly, the mixture is put into a quartz tube and vacuumized to 10 degrees-4Pa sealing the tube, placing the tube in a muffle furnace, slowly heating to 900 ℃, preserving heat for 72 hours, cooling to 400 ℃ at a speed of 5 ℃/h, closing the muffle furnace, and naturally cooling to room temperature to obtain the chemical formula of [ KBa ]2Cl][Ga4S8](space group: Pm). The obtained sample was named 8#。
Example 9 sample 9#Preparation of
Ba (68mg), Ga (171mg), S (142mg), RbCl (120mg), BaCl2(67mg) and after mixing uniformly, the mixture was put into a quartz tube and evacuated to 10 deg.f-4Pa sealing the tube, placing the tube in a muffle furnace, slowly heating to 900 ℃, preserving heat for 72 hours, cooling to 400 ℃ at the rate of 5 ℃/h, closing the muffle furnace, and naturally cooling to room temperature to obtain the chemical formula [ RbBa2Cl][Ga4S8](space group: Pm). The obtained sample was named 9#。
Example 10 sample 10#Preparation of
Ba (36mg), Ga (90mg), S (66mg), RbCl (127mg), BaCl2(78mg) and after mixing well, the mixture was put into a quartz tube and evacuated to 10 deg.C-4Pa sealing the tube, placing the tube in a muffle furnace, slowly heating to 900 ℃, preserving heat for 72 hours, cooling to 400 ℃ at the rate of 5 ℃/h, closing the muffle furnace, and naturally cooling to room temperature to obtain the chemical formula [ RbBa2Cl][Ga4S8](space group: Pmn21) The crystal of (4). The obtained sample was named 10#。
Example 11 sample 1#～10#Structural characterization of
Sample 1#～10#The phase analysis (XRD) of X-ray powder diffraction of (2) was carried out on a MiniFlex II X-ray diffractometer from Rigaku corporation, Cu target, K α radiation source (λ 0.154184nm)Sample 1 prepared in examples 1 to 10#～10#All samples were of high purity and high crystallinity. Sample 1#The experimental values and the simulated values of the XRD spectrum of (1) are shown in FIG. 2, and the XRD spectrum shows that the sample 1 is#Preparation obtained [ KBa3Cl2][Ga5S10]Crystal, space group is I-4. Sample 2#The experimental values and the simulation values of the XRD spectrum of (1) are shown in FIG. 3, and the XRD spectrum shows that the sample 2 is#Is [ RbBa ]3Cl2][Ga5S10]Crystal, space group is I-4. Sample No. 5#The experimental values and the simulated values of the XRD spectrum of (1) are shown in FIG. 4, and the XRD spectrum shows that the sample 5 is#Is [ CsBa ]3Cl2][Ga5S10]Crystal, space group is I-4. Sample No. 4#To prepare [ CsBa2Cl][Ga4S8]The crystal has a space group of Pm. Sample No. 5#Is [ CsBa ]2Cl][Ga4S8]Crystal, space group is I-4.
Sample 1#-10#The X-ray single crystal diffraction of (2) was performed on a Mercury CCD type single crystal diffractometer, Mo target, K α radiation source (λ 0.07107nm), test temperature 293K and structure analysis by Shelxl97 pair sample 1#-10#The XRD diffraction pattern obtained by fitting the single crystal data is highly consistent with the XRD diffraction pattern obtained by the experiment, and the obtained sample is proved to be a sample with high purity and high crystallinity.
Sample 1#～10#Fitting the single crystal data to obtain GaS4The super-tetrahedral structure is typically shown in FIG. 1, wherein the anionic group formed by Ga and S comprises T2 super-tetrahedral structure, four GaS4The tetrahedra are joined by a common point S to form a structure having four Ga-S six-membered rings. Sample 1#FIG. 6 shows a crystal structure diagram obtained by fitting single crystal data of (1)#Is [ KBa ]3Cl2][Ga5S10]Crystal, space group is I-4. Sample No. 4#FIG. 7 shows a crystal structure diagram obtained by fitting the single crystal data of (A) A. in sample 5#Is [ CsBa ]2Cl][Ga4S8]Crystal, space group is I-4. Sample No. 4#FIG. 8 shows a crystal structure diagram obtained by fitting the single crystal data of (1), sample 7#Is [ CsBa ]2Cl][Ga4S8]Crystal with space group Pmn21。
Example 11 sample 1#～10#Non-linear optical performance test of
Sample 1#～10#The frequency doubling experiment comprises the following specific steps: a laser beam having a wavelength of 1910nm generated by the OPO technique was used as a fundamental light to irradiate a crystal powder to be tested, and the intensity of the generated 955nm second harmonic was detected by a Charge Coupled Device (CCD). The sample to be detected and the standard sample AgGaS are mixed2Grinding respectively, and screening out crystals with different particle sizes of 30-50 nm, 50-75 nm, 75-100 nm, 100-150 nm and 150-200 nm by using a standard sieve. Samples with different grain diameters are respectively loaded, the samples are placed in a laser light path, a near infrared CCD detector is used for testing nonlinear optical frequency doubling signals under the laser intensity of 1910nm, and then the grain diameter is used as a horizontal coordinate, the tested nonlinear optical frequency doubling signals are used as a vertical coordinate for drawing, so that the size of the nonlinear optical performance of the crystal material and the phase matching condition of the crystal material are judged. Typical results are shown in FIG. 5, corresponding to sample 1#、2#、5#And a standard sample AgGaS2. FIG. 5 shows that the crystal has a large frequency multiplication coefficient, about AgGaS20.9 times of that of the formula I, and is in type I phase matching at 1910 nm.
Example 12 sample 1#～10#Laser damage threshold test of
Sample 1#～10#The laser damage threshold experiment comprises the following specific steps: using a Q-switched Nd: YAG solid laser generates 1064nm laser as light source to irradiate the tested crystal powder. Screening out the tested sample and reference AgGaS by a standard sieve2Crystals of different sizes in the range ofAnd respectively loading samples at the wavelength of 200 and 250nm, placing the samples in a 1064nm laser light path with the pulse width of 10ns, continuously increasing the power of the laser, observing the damage condition of the surface of the sample until the sample has a damage light spot, recording the power of the laser at the moment, measuring the size of the damage light spot, and calculating the laser damage threshold of the sample. TABLE I sample 1 at 1064nm#Sample 2#Sample No. 5#And AgGaS2Comparison of laser damage threshold of polycrystalline powder, sample 1#Sample 2#Sample No. 5#Respectively AgGaS229.5, 28, 38.75 times. TABLE II sample 6 at 1064nm#Sample 3#Sample 7#And AgGaS2Comparison of laser damage threshold for polycrystalline powder, sample 6#Sample 3#Sample 7#Respectively AgGaS237, 34.25, 31.25 times. TABLE III sample 8 at 1064nm#Sample 9#Sample No. 4#And AgGaS2Comparison of laser damage threshold for polycrystalline powder, sample 8#Sample 9#Sample No. 4#Respectively AgGaS236, 44, 40 times of. Indicating that the laser damage threshold of the polycrystalline powder is commercial AgGaS220-50 times of the total weight of the powder. Sample 10#Similar effects are obtained.
Watch 1
Watch two
Watch III
Although the present application has been described with reference to a few embodiments, it should be understood that various changes, substitutions and alterations can be made herein without departing from the spirit and scope of the application as defined by the appended claims.
Claims (10)
1. A second-order nonlinear optical material is characterized by having a chemical formula shown as a formula I:
ABaxX1+2x-mGamS2mformula I;
wherein A is selected from at least one of alkali metals, and X is selected from at least one of halogen elements;
x is 1, 2 or 3; m is any positive integer of 1, 2, 3, 4 or 5;
the second-order nonlinear optical material satisfies phase matching at least one wavelength of an infrared band.
2. The second order nonlinear optical material of claim 1, wherein the second order nonlinear optical material has a chemical formula shown in formula I':
[ABaxX1+2x-m][GamS2m]formula I';
wherein A is at least one of alkali metals, and X is at least one of halogen elements;
x is selected from 1, 2 or 3; m is selected from any positive integer of 1, 2, 3, 4 or 5;
the second-order nonlinear optical material satisfies phase matching at least one wavelength of an infrared band.
3. The second-order nonlinear optical material according to claim 1 or 2, wherein a is at least one selected from Na, K, Rb, Cs; x is selected from at least one of F, Cl, Br and I;
the second-order nonlinear optical material meets phase matching at least one wavelength of a near-infrared band;
preferably, the second order nonlinear optical material is type I phase matched at 1910 nm.
4. A second-order nonlinear optical material in accordance with claim 1 or 2, wherein the material belongs to the tetragonal I-4 space group, orthorhombic Pmn21Space group or a Pm space group of monoclinic system, and the unit cell parameters are as follows:and Z is 1 or 2.
5. The second order nonlinear optical material according to claim 1 or 2, wherein the second order nonlinear optical material is one of a material of formula II, a crystalline material of formula III;
[ABa3X2][Ga5S10]formula II;
a material of formula II belonging to the tetragonal system, space group I-4, having a unit cell parameter of b＝8.34～8.52，α＝90°，β＝90°，γ＝90°，Z＝2；
[ABa2X][Ga4S8]Formula III;
a material of formula III belonging to the orthorhombic system, space group Pmn21，b＝6.24～6.75，α＝90°，β＝90°，γ＝90°， Z＝2；
Or,
the material with the chemical formula of formula III belongs to a monoclinic system, a space group Pm,b＝6.55～7.97，α＝90°，β＝107.1～109.2°，γ＝90°，Z＝1。
6. a method for preparing a second-order nonlinear optical material according to any one of claims 1 to 5, comprising at least:
and heating a mixture containing barium element, gallium element, sulfur element, A element and X element to a reaction temperature under a vacuum condition, and reacting to obtain the second-order nonlinear optical material.
7. The method according to claim 6, characterized in that the following molar ratios are satisfied in the mixture:
Ba：Ga：S＝1～11：3～10：4～16；
preferably, the following molar ratios are satisfied in the mixture:
Ba：Ga：S：A：X＝1～11：3～10：4～16：1～20：1～20；
preferably, the following molar ratios are satisfied in the mixture:
Ba：Ga：S：A：X＝1：3：4～16：1～20：1～20；
preferably, the following molar ratios are satisfied in the mixture:
Ba：Ga：S：A：X＝1：4：4～16：1～20：1～20；
preferably, the following molar ratios are satisfied in the mixture:
Ba：Ga：S：A：X＝2～11：10：4～16：1～20：1～40；
preferably, the source of Ba in the mixture is selected from at least one of simple substance of barium, barium sulfide compound, and halide of barium;
the source of Ga in the mixture is selected from at least one of elementary gallium and gallium sulfide compounds;
the source of S in the mixture is selected from at least one of barium sulfide compound, gallium sulfide compound and sulfur powder;
the source of A in the mixture is selected from at least one of halides of A;
the source of X in the mixture is selected from at least one of halide of A and halide of barium;
preferably, the vacuum condition is 1Pa to 10 Pa-4Pa；
Preferably, the reaction condition is heating to 600-1100 ℃ and preserving heat, and the preserving heat time is not less than 1 hour;
further preferably, after the reaction is finished, the temperature is reduced to 100-500 ℃ at a speed of 1-10 ℃/h, and then the reaction product is naturally cooled.
8. Method according to claim 6, characterized in that it comprises at least:
raw materials containing barium, gallium, sulfur and AX are mixed according to a molar ratio of Ba: ga: s: AX is 1:3: (4-16): (1-20) mixing the materials according to the proportion, uniformly mixing, and keeping the vacuum degree at 1 Pa-10-4Heating to 600-1100 ℃ under the condition of Pa, and preserving heat for not less than 1 hour to obtain the second-order nonlinear optical material; the chemical formula is [ ABa3X2][Ga5S10](ii) a Or
Raw materials containing barium, gallium, sulfur and AX are mixed according to a molar ratio of Ba: ga: s: AX is 1: 4: (4-16): (1-20) mixing the materials according to the proportion, uniformly mixing, and keeping the vacuum degree at 1 Pa-10-4Heating to 600-1100 ℃ under the condition of Pa, and preserving heat for not less than 1 hour to obtain the second-order nonlinear optical material; the chemical formula is [ ABa2X][Ga4S8](ii) a Or
Raw materials containing barium, gallium, sulfur and AX are mixed according to a molar ratio of Ba: ga: s: AX: BaX21: 4: (4-16): (1-20): (1-10) mixing the materials according to the proportion, uniformly mixing, and keeping the vacuum degree at 1 Pa-10-4Heating to 600-1100 ℃ under the condition of Pa, and preserving heat for not less than 1 hour to obtain the second-order nonlinear optical material; the chemical formula is [ ABa2X][Ga4S8]。
9. Use of the second order nonlinear optical material of any one of claims 1 to 5 and/or the second order nonlinear optical material prepared by the method of any one of claims 6 to 8 in a laser.
10. An infrared nonlinear optical material comprising the second-order nonlinear optical material according to any one of claims 1 to 5 and/or the second-order nonlinear optical material prepared by the method according to any one of claims 6 to 8.
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| CN112575368A (en) * | 2019-09-30 | 2021-03-30 | 中国科学院福建物质结构研究所 | Gallium-containing nonlinear optical crystal material and synthesis method and application thereof |
| CN112575368B (en) * | 2019-09-30 | 2022-02-18 | 中国科学院福建物质结构研究所 | Gallium-containing nonlinear optical crystal material and synthesis method and application thereof |
| CN116024667A (en) * | 2021-10-25 | 2023-04-28 | 闽都创新实验室 | Inorganic compound crystal and preparation method and application thereof |
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