CN116240634A - Compound monoclinic phase selenium gallium barium and monoclinic phase selenium gallium barium nonlinear optical crystal, preparation method and application thereof - Google Patents
Compound monoclinic phase selenium gallium barium and monoclinic phase selenium gallium barium nonlinear optical crystal, preparation method and application thereof Download PDFInfo
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- 239000011669 selenium Substances 0.000 title claims abstract description 244
- 229910052711 selenium Inorganic materials 0.000 title claims abstract description 119
- BUGBHKTXTAQXES-UHFFFAOYSA-N Selenium Chemical compound [Se] BUGBHKTXTAQXES-UHFFFAOYSA-N 0.000 title claims abstract description 117
- 229910052733 gallium Inorganic materials 0.000 title claims abstract description 114
- GYHNNYVSQQEPJS-UHFFFAOYSA-N Gallium Chemical compound [Ga] GYHNNYVSQQEPJS-UHFFFAOYSA-N 0.000 title claims abstract description 111
- 239000013078 crystal Substances 0.000 title claims abstract description 106
- 229910052788 barium Inorganic materials 0.000 title claims abstract description 102
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 title claims abstract description 102
- 150000001875 compounds Chemical class 0.000 title claims abstract description 84
- 230000003287 optical effect Effects 0.000 title claims abstract description 54
- 238000002360 preparation method Methods 0.000 title claims description 13
- 239000012071 phase Substances 0.000 claims abstract description 87
- 239000000126 substance Substances 0.000 claims abstract description 56
- 239000000843 powder Substances 0.000 claims abstract description 42
- 238000003746 solid phase reaction Methods 0.000 claims abstract description 7
- 238000002425 crystallisation Methods 0.000 claims abstract description 3
- 230000008025 crystallization Effects 0.000 claims abstract description 3
- 238000010438 heat treatment Methods 0.000 claims description 74
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 71
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 44
- 239000010453 quartz Substances 0.000 claims description 44
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 38
- 229910002804 graphite Inorganic materials 0.000 claims description 38
- 239000010439 graphite Substances 0.000 claims description 38
- 238000007789 sealing Methods 0.000 claims description 29
- 239000011261 inert gas Substances 0.000 claims description 24
- 239000002994 raw material Substances 0.000 claims description 24
- 238000002441 X-ray diffraction Methods 0.000 claims description 22
- 229910052786 argon Inorganic materials 0.000 claims description 22
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 22
- 239000001301 oxygen Substances 0.000 claims description 22
- 229910052760 oxygen Inorganic materials 0.000 claims description 22
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 22
- 238000001816 cooling Methods 0.000 claims description 21
- 238000000034 method Methods 0.000 claims description 20
- 238000002156 mixing Methods 0.000 claims description 20
- 238000011049 filling Methods 0.000 claims description 16
- ZZEMEJKDTZOXOI-UHFFFAOYSA-N digallium;selenium(2-) Chemical compound [Ga+3].[Ga+3].[Se-2].[Se-2].[Se-2] ZZEMEJKDTZOXOI-UHFFFAOYSA-N 0.000 claims description 15
- 239000003795 chemical substances by application Substances 0.000 claims description 12
- 238000002083 X-ray spectrum Methods 0.000 claims description 11
- 238000000227 grinding Methods 0.000 claims description 11
- 238000005360 mashing Methods 0.000 claims description 11
- 239000004570 mortar (masonry) Substances 0.000 claims description 11
- 239000000463 material Substances 0.000 claims description 10
- 239000000203 mixture Substances 0.000 claims description 10
- RJWLRCHYHHXJLX-UHFFFAOYSA-N barium(2+);selenium(2-) Chemical compound [Se-2].[Ba+2] RJWLRCHYHHXJLX-UHFFFAOYSA-N 0.000 claims description 9
- NKQIMNKPSDEDMO-UHFFFAOYSA-L barium bromide Chemical compound [Br-].[Br-].[Ba+2] NKQIMNKPSDEDMO-UHFFFAOYSA-L 0.000 claims description 6
- 229910001620 barium bromide Inorganic materials 0.000 claims description 6
- WDIHJSXYQDMJHN-UHFFFAOYSA-L barium chloride Chemical compound [Cl-].[Cl-].[Ba+2] WDIHJSXYQDMJHN-UHFFFAOYSA-L 0.000 claims description 6
- 229910001626 barium chloride Inorganic materials 0.000 claims description 6
- OYLGJCQECKOTOL-UHFFFAOYSA-L barium fluoride Chemical compound [F-].[F-].[Ba+2] OYLGJCQECKOTOL-UHFFFAOYSA-L 0.000 claims description 6
- 229910001632 barium fluoride Inorganic materials 0.000 claims description 6
- 238000002844 melting Methods 0.000 claims description 5
- 230000008018 melting Effects 0.000 claims description 5
- 238000004891 communication Methods 0.000 claims description 3
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 claims description 2
- UPWPDUACHOATKO-UHFFFAOYSA-K gallium trichloride Chemical compound Cl[Ga](Cl)Cl UPWPDUACHOATKO-UHFFFAOYSA-K 0.000 claims description 2
- SRVXDMYFQIODQI-UHFFFAOYSA-K gallium(iii) bromide Chemical compound Br[Ga](Br)Br SRVXDMYFQIODQI-UHFFFAOYSA-K 0.000 claims description 2
- 239000002131 composite material Substances 0.000 claims 2
- CXMYWOCYTPKBPP-UHFFFAOYSA-N 3-(3-hydroxypropylamino)propan-1-ol Chemical compound OCCCNCCCO CXMYWOCYTPKBPP-UHFFFAOYSA-N 0.000 claims 1
- 239000003054 catalyst Substances 0.000 claims 1
- VIEXQFHKRAHTQS-UHFFFAOYSA-N chloroselanyl selenohypochlorite Chemical compound Cl[Se][Se]Cl VIEXQFHKRAHTQS-UHFFFAOYSA-N 0.000 claims 1
- LMDVZDMBPZVAIV-UHFFFAOYSA-N selenium hexafluoride Chemical compound F[Se](F)(F)(F)(F)F LMDVZDMBPZVAIV-UHFFFAOYSA-N 0.000 claims 1
- 238000006243 chemical reaction Methods 0.000 abstract description 22
- 230000000694 effects Effects 0.000 abstract description 5
- 238000004519 manufacturing process Methods 0.000 abstract description 5
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 abstract description 3
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 abstract description 3
- 229910052709 silver Inorganic materials 0.000 abstract description 3
- 239000004332 silver Substances 0.000 abstract description 3
- 230000005540 biological transmission Effects 0.000 abstract description 2
- 238000013467 fragmentation Methods 0.000 abstract 1
- 238000006062 fragmentation reaction Methods 0.000 abstract 1
- LBJNMUFDOHXDFG-UHFFFAOYSA-N copper;hydrate Chemical compound O.[Cu].[Cu] LBJNMUFDOHXDFG-UHFFFAOYSA-N 0.000 description 9
- 238000004458 analytical method Methods 0.000 description 8
- 238000004467 single crystal X-ray diffraction Methods 0.000 description 8
- 241001289141 Babr Species 0.000 description 6
- 229910016036 BaF 2 Inorganic materials 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000002050 diffraction method Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 238000000634 powder X-ray diffraction Methods 0.000 description 1
- 238000005086 pumping Methods 0.000 description 1
- -1 selenium gallium barium compound Chemical class 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
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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
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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
- C30B28/00—Production of homogeneous polycrystalline material with defined structure
- C30B28/02—Production of homogeneous polycrystalline material with defined structure directly from the solid state
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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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- Organic Chemistry (AREA)
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Abstract
The invention relates to a compound monoclinic phase selenium gallium barium and monoclinic phase selenium gallium barium nonlinear optical crystal, the chemical formulas are BaGa 4 Se 7 The compound and the crystal are monoclinic, the space group is Cc, and the unit cell parameter is
Beta= 97.749 (3) °, z=2, unit cell volume
Molecular weight 968.94. The compound monoclinic phase selenium gallium barium is synthesized by adopting high-temperature solid phase reaction under the vacuum condition; the monoclinic phase selenium gallium barium nonlinear optical crystal is synthesized by adopting a high Wen Zifa crystallization reaction under a vacuum condition; the BaGa 4 Se 7 The powder has the frequency doubling effect of silver gallium sulfide (AgGaS) under the same granularity under the irradiation of 2090nm laser 2 ) 3 times of (3); the BaGa 4 Se 7 The nonlinear optical crystal has the advantages of wider light transmission wave band, higher hardness, good mechanical property, difficult fragmentation and deliquescence, easy processing and storage and the like, and is used for manufacturing nonlinear optical devices.
Description
Technical Field
The invention relates to a compound with a chemical formula of BaGa 4 Se 7 The compound monoclinic phase selenium gallium barium and monoclinic phase selenium gallium barium nonlinear optical crystal, the preparation method of the crystal and the nonlinear optical device manufactured by the crystal.
Background
The novel nonlinear optical crystal with large frequency doubling effect, wide transmission wave band, large optical damage threshold and stable physical and chemical properties is explored, and is always a research hot spot in the field of laser frequency conversion. The main nonlinear optical materials at present are: beta-BaB 2 O 4 (BBO) crystal, liB 3 O 5 (LBO) Crystal, csB 3 O 5 (CBO) crystals, csLiB 6 O 10 (CLBO) Crystal and KBe 2 BO 3 F 2 (KBBF) crystals. Although the crystal growth techniques of these materials have grown to date, there are significant disadvantages: such as deliquescence, long growth period, serious lamellar growth habit, high price and the like. Therefore, finding new nonlinear optical crystal materials remains a very important and arduous task. In order to make up the defects of the nonlinear optical crystal, scientists in various countries are still focusing on the exploration and research of various novel nonlinear optical crystals, not only focusing on the optical performance and mechanical performance of the crystal, but also focusing on the preparation characteristics of the crystal.
So far, the generation of the 3-20 μm solid-state mid-far infrared band laser is mainly based on nonlinear optical principle and infrared nonlinear optical crystal frequency conversion technology. In the infrared nonlinear optical crystal market, the common infrared nonlinear optical crystal mainly comprises AgGaS 2 ，AgGaSe 2 ，ZnGeP 2 Etc. Although these crystals have been used in the civil production and living high-tech fields and military equipment, these crystal materials have their own drawbacks, and the comprehensive properties of these crystal materials cannot meet the ideal requirements of people, and as the technological development and requirements are improved, the demand for infrared nonlinear crystals with more excellent properties is more urgent, so that the exploration of novel mid-far infrared nonlinear crystals has important strategic significance in the civil high-tech industry and the improvement of military equipment, and the synthesis and growth of crystal materials with excellent properties are a great challenge in this direction.
Disclosure of Invention
The first object of the present invention is to provide a compound monoclinic phase selenium gallium barium, the chemical formula of the compound is BaGa 4 Se 7 The molecular weight is 968.94, the single crystal is of a non-central symmetrical structure, belongs to a monoclinic system, the space group is Cc, and the unit cell parameter is
Beta= 97.749 (3) °, z=2, unit cell volume
Preparing polycrystalline powder by adopting a high-temperature solid-phase reaction method.
Another object of the present invention is to provide a monoclinic phase selenium gallium barium nonlinear optical crystal and a preparation method thereof, wherein the chemical formula of the crystal is BaGa 4 Se 7 The molecular weight is 968.94, the single crystal is of a non-central symmetrical structure, belongs to a monoclinic system, the space group is Cc, and the unit cell parameter is
Beta= 97.749 (3) °, z=2, unit cell volume +.>
The preparation method comprises the solid phase reaction of simple substance barium and barium-containing compound, simple substance gallium and gallium-containing compound, simple substance selenium and selenium-containing compound under vacuum condition; the compound of the invention is monoclinic phase selenium gallium barium and monoclinic phase selenium gallium barium non-The powder of the linear optical crystal has a granularity of 55-88 μm of BaGa under 2090nm laser irradiation 4 Se 7 The frequency doubling effect is that of silver gallium sulfide (AgGaS) 2 ) 3 times of (3).
It is still another object of the present invention to provide the use of monoclinic phase selenogaba nonlinear optical devices for the fabrication of infrared communication devices, infrared band laser frequency doubling crystals, and infrared laser guidance device fabrication, up-frequency converters, down-frequency converters, or optical parametric oscillators.
The technical scheme of the invention is as follows:
the chemical formula of the compound monoclinic phase selenium gallium barium provided by the invention is BaGa 4 Se 7 The method comprises the steps of carrying out a first treatment on the surface of the The preparation process adopts a high-temperature solid phase reaction method, and the specific operation comprises the following steps:
a. uniformly mixing a barium-containing compound or a barium simple substance, a gallium-containing compound or a gallium simple substance, a selenium-containing compound or a selenium simple substance according to a molar ratio of 1:4:7 in a glove box filled with inert gas argon, wherein an airtight container with water content and oxygen content of 0.01-0.1ppm is filled with the inert gas, putting the mixture into a clean graphite crucible, filling the clean graphite crucible into a quartz glass tube, and placing the quartz tube filled with raw materials into a vacuum degree of 10 -5 -10 -1 Vacuumizing under Pa, and sealing;
b. c, heating the quartz tube sealed in the step a from room temperature to 400-700 ℃ at a heating rate of 10-40 ℃/h, preserving heat for 30-60 hours, heating to 800-1000 ℃ at a temperature of 20-40 ℃/h, and preserving heat for 70-110 hours;
c. cooling at 2-7deg.C/h to room temperature, taking out sample, mashing in mortar, and grinding to obtain compound BaGa 4 Se 7 Polycrystalline powder, performing X-ray analysis on the compound monoclinic phase selenium gallium barium polycrystalline powder to obtain an X-ray diffraction pattern and BaGa resolved by a single crystal structure 4 Se 7 The theoretical X-ray spectra are consistent.
The barium-containing compound comprises at least one of barium fluoride, barium chloride, barium bromide and barium selenide;
the gallium-containing compound comprises at least one of gallium fluoride, gallium chloride, gallium bromide and gallium selenide;
the selenium-containing compound is at least one of barium selenide and gallium selenide.
The monoclinic phase selenium gallium barium compound can be prepared by adopting a solid phase reaction method according to the following chemical reaction formula:
1)Ba+4Ga+7Se→BaGa 4 Se 7
2)Ba+2Ga 2 Se 3 +Se→BaGa 4 Se 7
3)BaSe+2Ga 2 Se 3 →BaGa 4 Se 7
4)BaF 2 +2Ga 2 Se 3 +1.5Se→BaGa 4 Se 7 +0.5SeF 4 ↑
5)BaF 2 +4Ga+7.5Se→BaGa 4 Se 7 +0.5SeF 4 ↑
6)BaCl 2 +2Ga 2 Se 3 +1.5Se→BaGa 4 Se 7 +0.5SeCl 4 ↑
7)BaCl 2 +4Ga+7.5Se→BaGa 4 Se 7 +0.5SeCl 4 ↑
8)BaBr 2 +2Ga 2 Se 3 +1.5Se→BaGa 4 Se 7 +0.5SeBr 4 ↑
9)BaBr 2 +4Ga+7.5Se→BaGa 4 Se 7 +0.5SeBr 4 ↑
the monoclinic phase selenium gallium barium nonlinear optical crystal is characterized in that the chemical formula of the crystal is BaGa 4 Se 7 The molecular weight is 968.94, the single crystal is of a non-central symmetrical structure, belongs to a monoclinic system, the space group is Cc, and the unit cell parameter is
Beta= 97.749 (3) °, z=2, unit cell volume
The powder frequency doubling effect is about 3 times AGS (AgGaS) 2 )。
The monoclinic phase selenium gallium barium nonlinear optical crystal provided by the invention adopts a tube sealing high-temperature solution method or a Bridgman method (Bridgman method), and the specific operation is carried out according to the following steps:
a. placing the compound monoclinic phase selenium gallium barium single-phase polycrystalline powder obtained in any one of claims 1-3 or the mixture of the compound monoclinic phase selenium gallium barium single-phase polycrystalline powder obtained in any one of claims 1-3 and fluxing agent in a clean graphite crucible in a glove box filled with inert gas argon in an airtight container with water content and oxygen content of 0.01-0.1ppm, filling the crucible into a quartz glass tube, and placing the quartz tube filled with raw materials in a vacuum degree of 10 -5 -10 -1 Vacuumizing under Pa, and sealing;
or directly placing barium-containing compound or barium simple substance, gallium-containing compound or gallium simple substance, selenium-containing compound or mixture of selenium simple substance and fluxing agent into clean graphite crucible, placing into quartz glass tube, vacuum-sealing the quartz tube with raw material at 10 deg.C -5 -10 -1 Vacuumizing under Pa, and sealing.
The fluxing agent mainly comprises selenium or self-fluxing agent containing selenium, such as Se and Ga 2 Se 3 BaSe, etc., and other complex fluxing agents, e.g. Se-Ga 2 Se 3 、Se-BaSe、Ga 2 Se 3 -BaSe、Se-Ga 2 Se 3 BaSe, etc.
b. C, heating the quartz tube sealed in the step a from room temperature to 400-700 ℃ at a heating rate of 10-40 ℃/h, preserving heat for 30-60 hours, heating to 900-1100 ℃ at a temperature of 20-40 ℃/h, and preserving heat for 70-110 hours;
c. cooling to room temperature at a rate of 2-5 deg.C/h to obtain BaGa 4 Se 7 And (5) a crystal.
Or placing the crucible containing the mixture prepared in the step a into a crystal growing furnace, slowly descending the crucible, and enabling the crucible to pass through a heating furnace with a certain temperature gradient, wherein the temperature of the heating furnace is controlled to be slightly higher than the melting point of the material; selecting proper heating zone, the material in the crucible is melted when the crucible passes through the heating zone, the crystal growing apparatus is vertically lowered at a speed of 0.1-10mm/h, when the crucible is continuously lowered, the temperature of the bottom of the crucible is firstly lowered below the melting point, and crystallization is started, and the crystal continuously grows along with the lowering of the crucible, and the growth period of the crystal is prolongedThe period is 5-20 days, and the BaGa is prepared 4 Se 7 And (5) a crystal.
The monoclinic phase selenium gallium barium nonlinear optical crystal is applied to the preparation of an infrared communication device, an infrared band laser frequency doubling crystal, the preparation of an infrared laser guidance device, an upper frequency converter, a lower frequency converter or an optical parametric oscillator.
The powder of the monoclinic phase selenium gallium barium and the monoclinic phase selenium gallium barium nonlinear optical crystal has granularity of 55-88 mu m of BaGa under the irradiation of 2090nm laser 4 Se 7 The frequency doubling effect is that of silver gallium sulfide (AgGaS) 2 ) 3 times of (3).
In the monoclinic phase selenium gallium barium nonlinear optical crystal structure, the valence of Ba atoms, ga atoms and Se atoms are respectively +2, +3-2.
Drawings
FIG. 1 shows the compound BaGa of the present invention 4 Se 7 X-ray powder diffraction pattern of (2);
FIG. 2 shows BaGa according to the invention 4 Se 7 A crystal structure diagram;
FIG. 3 shows BaGa according to the invention 4 Se 7 Working principle diagram of nonlinear optical device for crystal production, wherein 1 is laser, 2 is emitted light beam, 3 is BaGa 4 Se 7 The crystal, 4 is the outgoing light beam, 5 is the filter.
Detailed Description
The invention is illustrated in detail by the following examples, but is not limited to the examples given.
Example 1:
according to the reaction formula: ba+4Ga+7Se→BaGa 4 Se 7 Preparing compound monoclinic phase selenium gallium barium polycrystal powder:
a. uniformly mixing a barium simple substance, a gallium simple substance and a selenium simple substance according to a molar ratio of 1:4:7 in a glove box filled with inert gas argon, wherein an airtight container with water content and oxygen content of 0.05ppm is arranged in a clean graphite crucible, filling the crucible in a quartz glass tube, and placing the quartz tube filled with raw materials in a vacuum degree of 10 -3 Vacuumizing under Pa, and sealing;
b. c, heating the quartz tube sealed in the step a from room temperature to 400 ℃ at a heating rate of 10 ℃/h, preserving heat for 30 hours, heating to 800 ℃ at a temperature of 20 ℃/h, and preserving heat for 70 hours;
c. cooling at a rate of 2 deg.C/h to room temperature, taking out the sample, mashing in a mortar, and grinding to obtain pale yellow compound BaGa 4 Se 7 Polycrystalline powder, performing X-ray analysis on the compound monoclinic phase selenium gallium barium polycrystalline powder to obtain an X-ray diffraction pattern and BaGa resolved by a single crystal structure 4 Se 7 The theoretical X-ray spectra are consistent.
According to the reaction formula: ba+4Ga+7Se→BaGa 4 Se 7 Preparing a compound monoclinic phase selenium gallium barium nonlinear optical crystal:
a. placing a mixture of elementary barium, elementary gallium and elementary selenium in a molar ratio of 1:4:7 into a clean graphite crucible in a glove box filled with inert gas argon, wherein an airtight container with water content and oxygen content of 0.05ppm, filling the crucible into a quartz glass tube, and placing the quartz tube filled with raw materials into a vacuum degree of 10 -3 Vacuumizing under Pa, and sealing.
b. C, heating the quartz tube sealed in the step a from room temperature to 400 ℃ at a heating rate of 10 ℃/h, preserving heat for 30 hours, heating to 900 ℃ at a temperature of 20 ℃/h, and preserving heat for 70 hours;
c. cooling to room temperature at the rate of 2 ℃/h, taking out the graphite crucible to obtain yellowish blocky monoclinic phase selenium gallium barium BaGa 4 Se 7 The crystal is a monoclinic phase selenium gallium barium nonlinear optical crystal shown by single crystal X-ray diffraction analysis.
Example 2
According to the reaction formula: ba+2Ga 2 Se 3 +Se→BaGa 4 Se 7 Preparing compound monoclinic phase selenium gallium barium polycrystal powder:
a. uniformly mixing a barium simple substance, gallium selenide and a selenium simple substance according to a molar ratio of 1:2:1 in a glove box filled with inert gas argon, wherein an airtight container with water content and oxygen content of 0.05ppm is arranged in a quartz glass tube, putting the quartz glass tube filled with raw materials into a clean graphite crucible, and vacuum-pumping the quartz glass tube into a vacuum degree of 10 -3 Vacuumizing under Pa, and sealing;
b. c, heating the quartz tube sealed in the step a from room temperature to 700 ℃ at a heating rate of 40 ℃/h, preserving heat for 60 hours, heating to 1000 ℃ at the temperature of 40 ℃/h, and preserving heat for 110 hours;
c. cooling at a rate of 7deg.C/h to room temperature, taking out the sample, mashing in a mortar, and grinding to obtain pale yellow compound BaGa 4 Se 7 Polycrystalline powder, performing X-ray analysis on the compound monoclinic phase selenium gallium barium polycrystalline powder to obtain an X-ray diffraction pattern and BaGa resolved by a single crystal structure 4 Se 7 The theoretical X-ray spectra are consistent.
According to the reaction formula: ba+2Ga 2 Se 3 +Se→BaGa 4 Se 7 Preparing a compound monoclinic phase selenium gallium barium nonlinear optical crystal:
a. mixing the elementary substances of barium, gallium selenide and selenium in a molar ratio of 1:2:1 in a glove box filled with inert gas argon, wherein an airtight container with water content and oxygen content of 0.05ppm is placed in a clean graphite crucible, and then the crucible is placed in a quartz glass tube, and the quartz tube filled with raw materials is placed in a vacuum degree of 10 percent -3 Vacuumizing under Pa, and sealing.
b. C, heating the quartz tube sealed in the step a from room temperature to 700 ℃ at a heating rate of 40 ℃/h, preserving heat for 60 hours, heating to 1100 ℃ at the temperature of 40 ℃/h, and preserving heat for 110 hours;
c. cooling to room temperature at a speed of 5 ℃/h, taking out the graphite crucible to obtain yellowish blocky monoclinic phase selenium gallium barium BaGa 4 Se 7 The crystal is a monoclinic phase selenium gallium barium nonlinear optical crystal shown by single crystal X-ray diffraction analysis.
Example 3
According to the reaction formula: baSe+2Ga 2 Se 3 →BaGa 4 Se 7 Preparing compound monoclinic phase selenium gallium barium polycrystal powder:
a. uniformly mixing barium selenide and gallium selenide according to a molar ratio of 1:2 in a glove box with an airtight container filled with inert gas argon, wherein the airtight container has water content and oxygen content of 0.05ppm, putting the mixture into a clean graphite crucible, and filling quartzIn the glass tube, the quartz tube filled with the raw material was subjected to a vacuum of 10 -3 Vacuumizing under Pa, and sealing;
b. c, heating the quartz tube sealed in the step a from room temperature to 500 ℃ at a heating rate of 20 ℃/h, preserving heat for 40 hours, heating to 850 ℃ at a temperature of 30 ℃/h, and preserving heat for 80 hours;
c. cooling at a rate of 6deg.C/h to room temperature, taking out the sample, mashing in a mortar, and grinding to obtain pale yellow compound BaGa 4 Se 7 Polycrystalline powder, performing X-ray analysis on the compound monoclinic phase selenium gallium barium polycrystalline powder to obtain an X-ray diffraction pattern and BaGa resolved by a single crystal structure 4 Se 7 The theoretical X-ray spectra are consistent.
According to the reaction formula: ba+2Ga 2 Se 3 +Se→BaGa 4 Se 7 Preparing a compound monoclinic phase selenium gallium barium nonlinear optical crystal:
a. mixing barium selenide and gallium selenide at a molar ratio of 1:2 in a glove box filled with inert gas argon in an airtight container with water content and oxygen content of 0.06ppm, placing into a clean graphite crucible, placing into a quartz glass tube, and vacuum-sealing the quartz tube with raw materials at a vacuum degree of 10 -3 Vacuumizing under Pa, and sealing.
b. C, heating the quartz tube sealed in the step a from room temperature to 650 ℃ at a heating rate of 35 ℃/h, preserving heat for 35 hours, heating to 1050 ℃ at the temperature of 35 ℃/h, and preserving heat for 90 hours;
c. cooling to room temperature at the speed of 4 ℃/h, taking out the graphite crucible to obtain yellowish blocky monoclinic phase selenium gallium barium BaGa 4 Se 7 The crystal is a monoclinic phase selenium gallium barium nonlinear optical crystal shown by single crystal X-ray diffraction analysis.
Example 4
According to the reaction formula: baF (Baf) 2 +2Ga 2 Se 3 +1.5Se→BaGa 4 Se 7 +0.5SeF 4 Preparing compound monoclinic phase selenium gallium barium polycrystal powder ∈10:
a. in a glove box filled with inert gas argon, an airtight container with water content and oxygen content of 0.05ppmUniformly mixing barium fluoride, gallium selenide and selenium simple substance according to a molar ratio of 1:2:1.5, then placing into a clean graphite crucible, placing into a quartz glass tube, and placing the quartz tube filled with raw materials into a vacuum degree of 10 -3 Vacuumizing under Pa, and sealing;
b. c, heating the quartz tube sealed in the step a from room temperature to 600 ℃ at a heating rate of 30 ℃/h, preserving heat for 25 hours, heating to 900 ℃ at a temperature of 30 ℃/h, and preserving heat for 80 hours;
c. cooling at a rate of 6deg.C/h to room temperature, taking out the sample, mashing in a mortar, and grinding to obtain pale yellow compound BaGa 4 Se 7 Polycrystalline powder, performing X-ray analysis on the compound monoclinic phase selenium gallium barium polycrystalline powder to obtain an X-ray diffraction pattern and BaGa resolved by a single crystal structure 4 Se 7 The theoretical X-ray spectra are consistent.
According to the reaction formula: baF (Baf) 2 +2Ga 2 Se 3 +1.5Se→BaGa 4 Se 7 +0.5SeF 4 Preparing a compound monoclinic phase selenium gallium barium nonlinear optical crystal ∈r:
a. mixing barium fluoride, gallium selenide and selenium simple substance according to a molar ratio of 1:2:1.5 in a glove box filled with inert gas argon, wherein an airtight container with water content and oxygen content of 0.05ppm is placed in a clean graphite crucible, and then the graphite crucible is placed in a quartz glass tube, and the quartz tube filled with raw materials is placed in a vacuum degree of 10 -3 Vacuumizing under Pa, and sealing.
b. C, heating the quartz tube sealed in the step a from room temperature to 650 ℃ at a heating rate of 20 ℃/h, preserving heat for 30 hours, heating to 1000 ℃ at a temperature of 30 ℃/h, and preserving heat for 100 hours;
c. cooling to room temperature at a speed of 5 ℃/h, taking out the graphite crucible to obtain yellowish blocky monoclinic phase selenium gallium barium BaGa 4 Se 7 The crystal is a monoclinic phase selenium gallium barium nonlinear optical crystal shown by single crystal X-ray diffraction analysis.
Example 5
According to the reaction formula: baF (Baf) 2 +4Ga+7.5Se→BaGa 4 Se 7 +0.5SeF 4 Preparation of compound monoclinic phase selenium gallium barium polycrystal powderAnd (3) powder:
a. uniformly mixing barium fluoride, gallium simple substance and selenium simple substance according to a molar ratio of 1:4:7.5 in a glove box filled with inert gas argon, wherein an airtight container with water content and oxygen content of 0.05ppm is arranged in a quartz glass tube, placing the quartz glass tube into which raw materials are filled, and placing the quartz glass tube into a vacuum degree of 10 -3 Vacuumizing under Pa, and sealing;
b. c, heating the quartz tube sealed in the step a from room temperature to 500 ℃ at a heating rate of 25 ℃/h, preserving heat for 35 hours, heating to 850 ℃ at the temperature of 25 ℃/h, and preserving heat for 80 hours;
c. cooling at a rate of 5 deg.C/h to room temperature, taking out the sample, mashing in a mortar, and grinding to obtain pale yellow compound BaGa 4 Se 7 Polycrystalline powder, performing X-ray analysis on the compound monoclinic phase selenium gallium barium polycrystalline powder to obtain an X-ray diffraction pattern and BaGa resolved by a single crystal structure 4 Se 7 The theoretical X-ray spectra are consistent.
According to the reaction formula: baF (Baf) 2 +4Ga+7.5Se→BaGa 4 Se 7 +0.5SeF 4 Preparing a compound monoclinic phase selenium gallium barium nonlinear optical crystal ∈r:
a. mixing barium fluoride, gallium simple substance and selenium simple substance according to a molar ratio of 1:4:7.5 in a glove box filled with inert gas argon in an airtight container with water content and oxygen content of 0.05ppm, putting into a clean graphite crucible, filling into a quartz glass tube, and placing the quartz tube filled with raw materials into a vacuum degree of 10 -3 Vacuumizing under Pa, and sealing.
b. C, heating the quartz tube sealed in the step a from room temperature to 550 ℃ at a heating rate of 5 ℃/h, preserving heat for 50 hours, heating to 950 ℃ at a temperature of 25 ℃/h, and preserving heat for 90 hours;
c. cooling to room temperature at a speed of 3 ℃/h, taking out the graphite crucible to obtain yellowish blocky monoclinic phase selenium gallium barium BaGa 4 Se 7 The crystal is a monoclinic phase selenium gallium barium nonlinear optical crystal shown by single crystal X-ray diffraction analysis.
Example 6
According to the reaction formula: baCl 2 +2Ga 2 Se 3 +1.5Se→BaGa 4 Se 7 +0.5SeCl 4 Preparing compound monoclinic phase selenium gallium barium polycrystal powder ∈10:
a. uniformly mixing barium chloride, gallium selenide and selenium simple substances according to a molar ratio of 1:2:1.5 in a glove box filled with inert gas argon, wherein an airtight container with water content and oxygen content of 0.07ppm is arranged in a clean graphite crucible, filling the crucible in a quartz glass tube, and placing the quartz tube filled with raw materials in a vacuum degree of 10 -3 Vacuumizing under Pa, and sealing;
b. c, heating the quartz tube sealed in the step a from room temperature to 550 ℃ at a heating rate of 20 ℃/h, preserving heat for 40 hours, heating to 900 ℃ at a temperature of 30 ℃/h, and preserving heat for 75 hours;
c. cooling at a rate of 6deg.C/h to room temperature, taking out the sample, mashing in a mortar, and grinding to obtain pale yellow compound BaGa 4 Se 7 Polycrystalline powder, performing X-ray analysis on the compound monoclinic phase selenium gallium barium polycrystalline powder to obtain an X-ray diffraction pattern and BaGa resolved by a single crystal structure 4 Se 7 The theoretical X-ray spectra are consistent.
According to the reaction formula: baCl 2 +2Ga 2 Se 3 +1.5Se→BaGa 4 Se 7 +0.5SeCl 4 Preparing a compound monoclinic phase selenium gallium barium nonlinear optical crystal ∈r:
a. mixing barium chloride, gallium selenide and selenium simple substances according to a molar ratio of 1:2:1.5 in a glove box filled with inert gas argon, wherein an airtight container with water content and oxygen content of 0.04ppm is arranged in a clean graphite crucible, filling the graphite crucible in a quartz glass tube, and placing the quartz tube filled with raw materials in a vacuum degree of 10 -5 -10 -1 Vacuumizing under Pa, and sealing.
b. C, heating the quartz tube sealed in the step a from room temperature to 600 ℃ at a heating rate of 30 ℃/h, preserving heat for 50 hours, heating to 1050 ℃ at the temperature of 30 ℃/h, and preserving heat for 90 hours;
c. cooling to room temperature at the rate of 2 ℃/h, taking out the graphite crucible to obtain yellowish blocky monoclinic phase selenium gallium barium BaGa 4 Se 7 Crystals by single crystal X-rayLine diffraction analysis shows that the crystal is a monoclinic phase selenium gallium barium nonlinear optical crystal.
Example 7
According to the reaction formula: baCl 2 +4Ga+7.5Se→BaGa 4 Se 7 +0.5SeCl 4 Preparing compound monoclinic phase selenium gallium barium polycrystal powder ∈10:
a. uniformly mixing barium chloride, gallium simple substance and selenium simple substance according to a molar ratio of 1:4:7.5 in a glove box filled with inert gas argon, wherein an airtight container with water content and oxygen content of 0.06ppm is arranged in a clean graphite crucible, filling the crucible in a quartz glass tube, and placing the quartz tube filled with raw materials in a vacuum degree of 10 -3 Vacuumizing under Pa, and sealing;
b. c, heating the quartz tube sealed in the step a from room temperature to 500 ℃ at a heating rate of 20 ℃/h, preserving heat for 50 hours, heating to 850 ℃ at a temperature of 30 ℃/h, and preserving heat for 90 hours;
c. cooling at a rate of 5 deg.C/h to room temperature, taking out the sample, mashing in a mortar, and grinding to obtain pale yellow compound BaGa 4 Se 7 Polycrystalline powder, performing X-ray analysis on the compound monoclinic phase selenium gallium barium polycrystalline powder to obtain an X-ray diffraction pattern and BaGa resolved by a single crystal structure 4 Se 7 The theoretical X-ray spectra are consistent.
According to the reaction formula: baCl 2 +4Ga+7.5Se→BaGa 4 Se 7 +0.5SeCl 4 Preparing a compound monoclinic phase selenium gallium barium nonlinear optical crystal ∈r:
a. mixing barium chloride, gallium simple substance and selenium simple substance according to a molar ratio of 1:4:7.5 in a glove box filled with inert gas argon in an airtight container with water content and oxygen content of 0.01-0.1ppm, putting into a clean graphite crucible, filling into a quartz glass tube, and placing the quartz tube filled with raw materials into a vacuum degree of 10 -5 -10 -1 Vacuumizing under Pa, and sealing.
b. C, heating the quartz tube sealed in the step a from room temperature to 600 ℃ at a heating rate of 30 ℃/h, preserving heat for 30 hours, heating to 1150 ℃ at a temperature of 30 ℃/h, and preserving heat for 90 hours;
c. at a rate of 4 ℃/hCooling to room temperature, taking out the graphite crucible to obtain yellowish blocky monoclinic phase selenium gallium barium BaGa 4 Se 7 The crystal is a monoclinic phase selenium gallium barium nonlinear optical crystal shown by single crystal X-ray diffraction analysis.
Example 8
According to the reaction formula: baBr 2 +2Ga 2 Se 3 +1.5Se→BaGa 4 Se 7 +0.5SeBr 4 Preparing compound monoclinic phase selenium gallium barium polycrystal powder ∈10:
a. uniformly mixing barium bromide, gallium selenide and selenium simple substances according to a molar ratio of 1:2:1.5 in a glove box filled with inert gas argon, wherein an airtight container with water content and oxygen content of 0.05ppm is arranged in a clean graphite crucible, filling the graphite crucible in a quartz glass tube, and placing the quartz tube filled with raw materials in a vacuum degree of 10 -3 Vacuumizing under Pa, and sealing;
b. c, heating the quartz tube sealed in the step a from room temperature to 600 ℃ at a heating rate of 30 ℃/h, preserving heat for 40 hours, heating to 1000 ℃ at a temperature of 25 ℃/h, and preserving heat for 80 hours;
c. cooling at a rate of 3 deg.C/h to room temperature, taking out the sample, mashing in a mortar, and grinding to obtain pale yellow compound BaGa 4 Se 7 Polycrystalline powder, performing X-ray analysis on the compound monoclinic phase selenium gallium barium polycrystalline powder to obtain an X-ray diffraction pattern and BaGa resolved by a single crystal structure 4 Se 7 The theoretical X-ray spectra are consistent.
According to the reaction formula: baBr 2 +2Ga 2 Se 3 +1.5Se→BaGa 4 Se 7 +0.5SeBr 4 Preparing a compound monoclinic phase selenium gallium barium nonlinear optical crystal ∈r:
a. mixing barium bromide, gallium selenide and selenium simple substance according to a molar ratio of 1:2:1.5 in a glove box filled with inert gas argon, wherein an airtight container with water content and oxygen content of 0.03ppm is arranged in a clean graphite crucible, filling the graphite crucible in a quartz glass tube, and placing the quartz tube filled with raw materials in a vacuum degree of 10 -3 Vacuumizing under Pa, and sealing.
b. C, heating the quartz tube sealed in the step a from room temperature to 700 ℃ at a heating rate of 20 ℃/h, preserving heat for 60 hours, heating to 1100 ℃ at a temperature of 30 ℃/h, and preserving heat for 90 hours;
c. cooling to room temperature at the rate of 2 ℃/h, taking out the graphite crucible to obtain yellowish blocky monoclinic phase selenium gallium barium BaGa 4 Se 7 The crystal is a monoclinic phase selenium gallium barium nonlinear optical crystal shown by single crystal X-ray diffraction analysis.
Example 9
According to the reaction formula: baBr 2 +4Ga+7.5Se→BaGa 4 Se 7 +0.5SeBr 4 Preparing compound monoclinic phase selenium gallium barium polycrystal powder ∈10:
a. uniformly mixing barium bromide, elemental gallium and elemental selenium according to a molar ratio of 1:4:7.5 in a glove box filled with inert gas argon, wherein an airtight container with water content and oxygen content of 0.06ppm is arranged in a clean graphite crucible, filling the crucible in a quartz glass tube, and placing the quartz tube filled with raw materials in a vacuum degree of 10 -3 Vacuumizing under Pa, and sealing;
b. c, heating the quartz tube sealed in the step a from room temperature to 700 ℃ at a heating rate of 20 ℃/h, preserving heat for 30 hours, heating to 900 ℃ at a temperature of 20 ℃/h, and preserving heat for 80 hours;
c. cooling at a rate of 3 deg.C/h to room temperature, taking out the sample, mashing in a mortar, and grinding to obtain pale yellow compound BaGa 4 Se 7 Polycrystalline powder, performing X-ray analysis on the compound monoclinic phase selenium gallium barium polycrystalline powder to obtain an X-ray diffraction pattern and BaGa resolved by a single crystal structure 4 Se 7 The theoretical X-ray spectra are consistent.
According to the reaction formula: baBr 2 +4Ga+7.5Se→BaGa 4 Se 7 +0.5SeBr 4 Preparing a compound monoclinic phase selenium gallium barium nonlinear optical crystal ∈r:
a. mixing barium bromide, gallium simple substance and selenium simple substance according to a molar ratio of 1:4:7.5 in a glove box filled with inert gas argon in an airtight container with water content and oxygen content of 0.05ppm, putting into a clean graphite crucible, filling into a quartz glass tube, and placing the quartz tube filled with raw materials into a vacuum degree of 10 -5 -10 -1 Vacuumizing under Pa, and sealing.
b. C, heating the quartz tube sealed in the step a from room temperature to 700 ℃ at a heating rate of 20 ℃/h, preserving heat for 30 hours, heating to 1100 ℃ at a temperature of 20 ℃/h, and preserving heat for 90 hours;
c. cooling to room temperature at the rate of 2 ℃/h, taking out the graphite crucible to obtain yellowish blocky monoclinic phase selenium gallium barium BaGa 4 Se 7 The crystal is a monoclinic phase selenium gallium barium nonlinear optical crystal shown by single crystal X-ray diffraction analysis.
Example 10
The monoclinic phase selenium gallium barium nonlinear optical crystal obtained in any one of examples 1 to 9 was placed at the position 3 as shown in FIG. 3, a Q-switched Nd-YAG laser was used as a light source at room temperature, the incident wavelength was 2090nm, and an infrared beam 2 having a wavelength of 2090nm was emitted from the Q-switched Nd-YAG laser 1 and was incident on BaGa 4 Se 7 The single crystal 3 generates frequency doubling light with the wavelength of 1045nm, the output intensity is 3 times of that of AGS with the same condition, the outgoing light beam 4 contains infrared light with the wavelength of 2090nm and light with the wavelength of 1045nm, and the frequency doubling light with the wavelength of 1045nm is obtained after filtering by the filter 5.
Claims (8)
1. A compound monoclinic phase selenium gallium barium is characterized in that the chemical formula of the compound is BaGa 4 Se 7 Molecular weight 968.94, monoclinic system, space group Cc, unit cell parameters
Z=2, unit cell volume->
Is polycrystalline powder.
2. The method for preparing the compound monoclinic phase selenium gallium barium according to claim 1, which is characterized by comprising the following steps: mixing a barium-containing compound or a barium simple substance, a gallium-containing compound or a gallium simple substance, a selenium-containing compound or a selenium simple substance, and preparing the compound monoclinic phase selenium gallium barium by adopting a solid phase reaction method. Wherein, the molar ratio of the element barium in the barium-containing compound or the barium simple substance to the element gallium in the gallium-containing compound or the gallium simple substance to the element selenium in the selenium-containing compound or the selenium simple substance is 1-1.1:4-4.1:7-7.5.
The barium-containing compound comprises at least one of barium fluoride, barium chloride, barium bromide and barium selenide;
the gallium-containing compound comprises at least one of gallium fluoride, gallium chloride, gallium bromide and gallium selenide;
the selenium-containing compound is at least one of barium selenide and gallium selenide.
3. The method for preparing the compound monoclinic phase selenium gallium barium according to claim 2, which is characterized in that the compound monoclinic phase selenium gallium barium is prepared by adopting a high-temperature solid-phase reaction method, and the process comprises the following steps:
a. uniformly mixing a barium-containing compound or a barium simple substance, a gallium-containing compound or a gallium simple substance, a selenium-containing compound or a selenium simple substance according to a molar ratio of 1:4:7 in a glove box filled with inert gas argon, wherein an airtight container with water content and oxygen content of 0.01-0.1ppm is filled with the inert gas, putting the mixture into a clean graphite crucible, filling the clean graphite crucible into a quartz glass tube, and placing the quartz tube filled with raw materials into a vacuum degree of 10 -5 -10 - 1 Vacuumizing under Pa, and sealing;
b. c, heating the quartz tube sealed in the step a from room temperature to 400-700 ℃ at a heating rate of 10-40 ℃/h, preserving heat for 30-60 hours, heating to 800-1000 ℃ at a temperature of 20-40 ℃/h, and preserving heat for 70-100 hours;
c. cooling at 2-7deg.C/h to room temperature, taking out sample, mashing in mortar, and grinding to obtain compound BaGa 4 Se 7 Polycrystalline powder, performing X-ray analysis on the compound monoclinic phase selenium gallium barium polycrystalline powder to obtain an X-ray diffraction pattern and BaGa resolved by a single crystal structure 4 Se 7 The theoretical X-ray spectra are consistent.
4. A monoclinic phase barium selenide nonlinear optical crystal is characterized in that the chemical formula of the crystal is BaGa 4 Se 7 Molecular weight 968.94, monoclinic system, cc space group, unit cell parameters
Z=2, unit cell volume->
5. The method for preparing the barium selenide nonlinear optical crystal according to claim 4, wherein the preparation is carried out by a tube sealing high-temperature solution method or a Bridgman method (Bridgman method), and the method comprises the following steps:
a. placing the compound monoclinic phase selenium gallium barium single-phase polycrystalline powder obtained in any one of claims 1-3 or the mixture of the compound monoclinic phase selenium gallium barium single-phase polycrystalline powder obtained in any one of claims 1-3 and fluxing agent in a clean graphite crucible in a glove box filled with inert gas argon in an airtight container with water content and oxygen content of 0.01-0.1ppm, filling the crucible into a quartz glass tube, and placing the quartz tube filled with raw materials in a vacuum degree of 10 -5 -10 -1 Vacuumizing under Pa, and sealing;
or directly placing barium-containing compound or barium simple substance, gallium-containing compound or gallium simple substance, selenium-containing compound or mixture of selenium simple substance and fluxing agent into clean graphite crucible, placing into quartz glass tube, vacuum-sealing the quartz tube with raw material at 10 deg.C -5 -10 -1 Vacuumizing under Pa, and sealing.
b. C, heating the quartz tube sealed in the step a from room temperature to 400-700 ℃ at a heating rate of 10-40 ℃/h, preserving heat for 30-60 hours, heating to 900-1100 ℃ at a temperature of 20-40 ℃/h, and preserving heat for 70-110 hours;
c. cooling to room temperature at a rate of 2-5 deg.C/h to obtain BaGa 4 Se 7 And (5) a crystal.
Or placing the crucible containing the mixture prepared in the step a into a crystal growing furnace, slowly descending the crucible, and enabling the crucible to pass through a heating furnace with a certain temperature gradient, wherein the temperature of the heating furnace is controlled to be slightly higher than the melting point of the material; selecting proper heating area, melting the material in the crucible while the crucible passes through the heating area, vertically descending the crystal growing apparatus at 0.1-10mm/h, when the crucible continuously descends, lowering the temperature of the bottom of the crucible to below the melting point, and starting crystallization, wherein the crystal continuously grows along with the descending of the crucible, and the growth period is 5-20 days, thus obtaining the BaGa 4 Se 7 And (5) a crystal.
6. The method of claim 5, wherein the molar ratio of the compound monoclinic phase selenium gallium barium single-phase polycrystalline powder to the fluxing agent is 1-1.2:0-20; or wherein the molar ratio of the barium-containing compound or the barium simple substance, the gallium-containing compound or the gallium simple substance, the selenium-containing compound or the selenium simple substance to the fluxing agent is 1-1.1:4-4.1:7-7.5:0-20; the fluxing agent comprises at least one of selenium simple substance, gallium selenide, barium selenide, selenium fluoride, selenium chloride and selenium bromide, and one or more of the following composite fluxing agents:
Se-Ga 2 Se 3 、Se-BaSe、Se-Ga 2 Se 3 -BaSe、SeF 4 -Ga 2 Se 3 、SeF 4 -BaSe、SeF 4 -Ga 2 Se 3 -BaSe、SeCl 4 -Ga 2 Se 3 、SeCl 4 -BaSe、SeCl 4 -Ga 2 Se 3 -BaSe、SeBr 4 -Ga 2 Se 3 、SeBr 4 -BaSe、SeBr 4 -Ga 2 Se 3 -BaSe、Se-SeF 4 、Se-SeCl 4 、Se-SeBr 4 、Ga 2 Se 3 -BaSe。
7. the method according to claim 6, wherein the composite fluxing agent Se-Ga 2 Se 3 Se and Ga in the system 2 Se 3 The molar ratio of (2) is 1-3:1-3; the molar ratio of Se to BaSe in the Se-BaSe system is 1-3:1-2；Se-Ga 2 Se 3 se, ga in BaSe System 2 Se 3 The molar ratio of the active component to BaSe is 1-3:1-3:1-2; seF (SeF) 4 -Ga 2 Se 3 SeF in System 4 With Ga 2 Se 3 The molar ratio of (2) is 1-3:1-3; seF (SeF) 4 SeF in BaSe System 4 The molar ratio of the active component to BaSe is 1-3:1-2; seF (SeF) 4 -Ga 2 Se 3 SeF in BaSe System 4 、Ga 2 Se 3 The molar ratio of the active component to BaSe is 1-3:1-3:1-2; seCl 4 -Ga 2 Se 3 SeCl in System 4 With Ga 2 Se 3 The molar ratio of (2) is 1-3:1-3; seCl 4 SeCl in BaSe System 4 The molar ratio of the active component to BaSe is 1-3:1-2; seCl 4 -Ga 2 Se 3 SeCl in BaSe System 4 、Ga 2 Se 3 The molar ratio of the catalyst to the BaSe is 1-3:1-3:1-2.
8. The use of the monoclinic phase selenogaba nonlinear optical crystal according to claim 4, wherein the monoclinic phase selenogaba nonlinear optical crystal is used in the preparation of infrared communication devices, infrared band laser frequency doubling crystals, infrared laser guidance device preparation, up-frequency converters, down-frequency converters, or optical parametric oscillators.
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