CN114457427A - Selenium gallium lithium middle and far infrared nonlinear optical crystal and preparation method and application thereof - Google Patents
Selenium gallium lithium middle and far infrared nonlinear optical crystal and preparation method and application thereof Download PDFInfo
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- 239000013078 crystal Substances 0.000 title claims abstract description 119
- 239000011669 selenium Substances 0.000 title claims abstract description 96
- 230000003287 optical effect Effects 0.000 title claims abstract description 87
- 229910052711 selenium Inorganic materials 0.000 title claims abstract description 54
- BUGBHKTXTAQXES-UHFFFAOYSA-N Selenium Chemical compound [Se] BUGBHKTXTAQXES-UHFFFAOYSA-N 0.000 title claims abstract description 50
- PVAKBHJQBIKTDC-UHFFFAOYSA-N gallium lithium Chemical compound [Li].[Ga] PVAKBHJQBIKTDC-UHFFFAOYSA-N 0.000 title claims abstract description 50
- 238000002360 preparation method Methods 0.000 title claims abstract description 12
- 238000000034 method Methods 0.000 claims abstract description 31
- 238000006243 chemical reaction Methods 0.000 claims abstract description 14
- 238000002425 crystallisation Methods 0.000 claims abstract description 11
- 230000002269 spontaneous effect Effects 0.000 claims abstract description 11
- 239000000126 substance Substances 0.000 claims abstract description 8
- 229910005543 GaSe Inorganic materials 0.000 claims abstract description 5
- 238000004891 communication Methods 0.000 claims abstract description 5
- 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 abstract description 5
- 238000001514 detection method Methods 0.000 claims abstract description 5
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 36
- 238000010438 heat treatment Methods 0.000 claims description 20
- 238000001816 cooling Methods 0.000 claims description 16
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 13
- 239000010439 graphite Substances 0.000 claims description 13
- 229910002804 graphite Inorganic materials 0.000 claims description 13
- 238000002844 melting Methods 0.000 claims description 12
- 238000007789 sealing Methods 0.000 claims description 12
- 230000008018 melting Effects 0.000 claims description 11
- 239000010453 quartz Substances 0.000 claims description 11
- 239000002994 raw material Substances 0.000 claims description 10
- 238000000137 annealing Methods 0.000 claims description 7
- 229910052733 gallium Inorganic materials 0.000 claims description 7
- 238000002156 mixing Methods 0.000 claims description 7
- 238000005086 pumping Methods 0.000 claims description 7
- 229910052744 lithium Inorganic materials 0.000 claims description 4
- 150000001875 compounds Chemical class 0.000 claims description 3
- 239000000203 mixture Substances 0.000 claims description 2
- 238000002474 experimental method Methods 0.000 claims 1
- 238000010521 absorption reaction Methods 0.000 abstract description 4
- 239000000463 material Substances 0.000 description 5
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 4
- 102000003960 Ligases Human genes 0.000 description 3
- 108090000364 Ligases Proteins 0.000 description 3
- 230000005540 biological transmission Effects 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000012071 phase Substances 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 229910019142 PO4 Inorganic materials 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 2
- 238000005303 weighing Methods 0.000 description 2
- BTBUEUYNUDRHOZ-UHFFFAOYSA-N Borate Chemical compound [O-]B([O-])[O-] BTBUEUYNUDRHOZ-UHFFFAOYSA-N 0.000 description 1
- GYHNNYVSQQEPJS-UHFFFAOYSA-N Gallium Chemical compound [Ga] GYHNNYVSQQEPJS-UHFFFAOYSA-N 0.000 description 1
- 229910013321 LiB3O5 Inorganic materials 0.000 description 1
- 229910052775 Thulium Inorganic materials 0.000 description 1
- 229910007475 ZnGeP2 Inorganic materials 0.000 description 1
- 229910001413 alkali metal ion Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 229910001420 alkaline earth metal ion Inorganic materials 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 150000004770 chalcogenides Chemical class 0.000 description 1
- DVRDHUBQLOKMHZ-UHFFFAOYSA-N chalcopyrite Chemical group [S-2].[S-2].[Fe+2].[Cu+2] DVRDHUBQLOKMHZ-UHFFFAOYSA-N 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000012612 commercial material Substances 0.000 description 1
- 238000002447 crystallographic data Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- ZZEMEJKDTZOXOI-UHFFFAOYSA-N digallium;selenium(2-) Chemical compound [Ga+3].[Ga+3].[Se-2].[Se-2].[Se-2] ZZEMEJKDTZOXOI-UHFFFAOYSA-N 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- ZVSWQJGHNTUXDX-UHFFFAOYSA-N lambda1-selanyllithium Chemical compound [Se].[Li] ZVSWQJGHNTUXDX-UHFFFAOYSA-N 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000013307 optical fiber Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 238000000634 powder X-ray diffraction Methods 0.000 description 1
- 238000001144 powder X-ray diffraction data Methods 0.000 description 1
- 238000003746 solid phase reaction Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 229910019655 synthetic inorganic crystalline material Inorganic materials 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 238000001845 vibrational spectrum Methods 0.000 description 1
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- C30—CRYSTAL GROWTH
- C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
- C30B29/00—Single crystals or homogeneous polycrystalline material with defined structure characterised by the material or by their shape
- C30B29/10—Inorganic compounds or compositions
- C30B29/46—Sulfur-, selenium- or tellurium-containing compounds
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- C—CHEMISTRY; METALLURGY
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- 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
- C30B11/00—Single-crystal growth by normal freezing or freezing under temperature gradient, e.g. Bridgman-Stockbarger method
- C30B11/002—Crucibles or containers for supporting the melt
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- 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
- C30B33/00—After-treatment of single crystals or homogeneous polycrystalline material with defined structure
- C30B33/02—Heat treatment
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- 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
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Abstract
The invention relates to a selenium gallium lithium middle and far infrared nonlinear optical crystal and a preparation method and application thereof, wherein the chemical formula of the crystal is LiGaSe2Molecular weight of 469.16, crystallized in tetragonal system, and space group of non-centrosymmetric space groupI 
2dWith cell parameters ofa=5.843（2）Å，b=5.843（2）Å，c=10.614（8）Å，α=β=γ=90°，Z=2，V=362.4（4）Å3. Prepared by a high-temperature melt spontaneous crystallization method or a Bridgman method, and the structure of the crystal is formed by LiSe4]And [ GaSe ]4]The tetrahedron is formed, and can be used for preparing conversion of infrared band laser frequency, infrared laser guidance, infrared laser radar, energy detection, remote laser communication and the like. The obtained selenium gallium lithium mid-far infrared nonlinear optical crystal has excellent optical performance (long infrared absorption edge and large nonlinear coefficient). Has important application value in an infrared laser system.
Description
Technical Field
The invention relates to a selenium-gallium-lithium middle and far infrared nonlinear optical crystal, a preparation method and application thereof, belonging to the field of infrared nonlinear optical crystals
Background
Nonlinear optical crystals have attracted a great deal of attention from researchers in the laser field as frequency conversion devices in solid-state lasers. The infrared nonlinear optical crystal plays an important role in practical application, such as laser orientation, resource detection, long-distance laser communication and the like. Conventional nonlinear optical crystals such as borate (. beta. -BaB)2O4(BBO)、LiB3O5(LBO)、CsLiB6O10(CLBO)、KBe2BO3F2(KBBF)), phosphate (KH)2PO4(KDP)、KTiOPO4(KTP)) are widely used in the ultraviolet and visible light ranges, but their use in the mid and far infrared bands is limited due to small non-linear coefficients, short ir cut-off edges. The infrared nonlinear optical crystal commercialized at present is AgGaS2、AgGaSe2And ZnGeP2The materials have large nonlinear optical effects and wide transmission windows, but because intrinsic defects exist, such as low laser damage threshold, serious two-photon absorption near 1 μm and the like, the application of the materials in the current high-power laser output field is limited, the requirements of the current laser technology development cannot be completely met, and the development and design of novel infrared nonlinear optical crystal materials with large frequency multiplication, wide wavelength band and high laser damage threshold are urgently needed.
The ideal infrared nonlinear optical crystal material needs to meet the following basic requirements besides the necessary non-centrosymmetric structure: (1) large nonlinear optical coefficients; (2) a wide transmission window in an infrared band; (3) a higher laser damage threshold; (4) appropriate birefringence required to achieve phase matching; (5) certain mechanical strength and physical and chemical stability; (6) is easy to obtainLarge-size single crystals with good optical uniformity and the like are obtained. Practice proves that: in the chalcogenides system, the metal M of the third main group (M ═ Al, Ga) can form distorted [ MQ [ ]4](Q-S, Se) tetrahedra, thereby easily generating a non-centrosymmetric structure and showing a large nonlinear optical effect. In addition, the introduction of alkali metal and alkaline earth metal ions can not only expand the light-transmitting wave band, but also is beneficial to increasing the band gap of the compound. We utilized AgGaS2The crystal structure of [ LiSe ] is selected as a template4]And [ GaSe ]4]Tetrahedral substitution [ AgS ]4]And [ GaS ]4]Successfully synthesizes an example of frequency doubling effect about the current commercial AgGaS through high-temperature solid-phase reaction2Twice of the new mid-infrared nonlinear optical crystal material selenium gallium lithium.
Disclosure of Invention
The invention aims to provide a selenium gallium lithium middle and far infrared nonlinear optical crystal, a preparation method and application thereof, wherein the chemical formula of the crystal is LiGaSe2Molecular weight of 469.16, belonging to tetragonal system, space group of
Cell parameters of
α＝β＝γ＝90°，Z＝2，
The selenium gallium lithium mid-infrared nonlinear optical crystal is prepared by a high-temperature melt spontaneous crystallization method or a Bridgman method, and has wide application in conversion of infrared band laser frequency, infrared laser guidance, infrared laser radar, energy detection and remote laser communication. The obtained selenium-gallium-lithium mid-far infrared nonlinear optical crystal has excellent optical performance and infrared performanceThe absorption cut-off side length is long, and the nonlinear optical coefficient is large.
The invention relates to a selenium gallium lithium middle and far infrared nonlinear optical crystal, the chemical formula of which is LiGaSe2Molecular weight of 469.16, belonging to tetragonal system, space group of
Cell parameters of
α＝β＝γ＝90°，Z＝2，
The crystal structure is formed by [ LiSe4]And [ GaSe ]4]The tetrahedral element is formed, and the experimental band gap of the tetrahedral element is 1.71 eV.
The preparation method of the selenium gallium lithium mid-infrared nonlinear optical crystal adopts a high-temperature melt spontaneous crystallization method or a Bridgman method, and the specific operation is carried out according to the following steps:
the high-temperature melt spontaneous crystallization method for growing the selenium-gallium-lithium infrared nonlinear optical crystal comprises the following specific operations:
a. li or Li as Li raw material2Ga or Ga as Se or Ga raw material2Se3Respectively and uniformly mixing with Se, putting into a clean graphite crucible, then putting into a quartz glass tube, and pumping the quartz glass tube to 10 DEG by a vacuum pump-5-10-3Carrying out melting sealing after Pa vacuum degree;
b. putting the quartz glass tube in the step a into a muffle furnace controlled by a program, heating to 880-900 ℃ within 30-50 hours, and preserving heat for 40-50 hours;
c. then slowly cooling to room temperature at the speed of 3-5 ℃/h to obtain the selenium gallium lithium medium and far infrared nonlinear optical crystal;
the method for growing the selenium-gallium-lithium infrared nonlinear optical crystal by the Bridgman-Stockbarge method comprises the following specific operations:
a. taking Li as raw material2Se; ga as the raw material is Ga or Ga2Se3(ii) a Se raw material is Se simple substance or Se-containing compound, which is uniformly mixed, put into a clean graphite crucible, then put into a quartz glass tube, and the quartz glass tube is pumped to 10 degrees by a vacuum pump-5-10-3Carrying out melting sealing after Pa vacuum degree;
b. b, placing the sealed quartz tube in the step a into a crucible descending furnace, raising the temperature to 880-900 ℃ at the heating rate of 20-40 ℃/h, and preserving the temperature for 40-50 h;
c, vertically descending at the speed of 0.1-10mm/h, carrying out selenium gallium lithium infrared nonlinear optical crystal growth in the descending process of the crystal growth device, wherein the growth period is 10-40 days, after the crystal growth is finished, keeping the crystal in a growth furnace for annealing, and cooling to the room temperature at the speed of 10-80 ℃/h to obtain the selenium gallium lithium infrared nonlinear optical crystal.
The selenium gallium lithium mid-far infrared nonlinear optical crystal is used for preparing infrared band laser frequency conversion, infrared laser guidance, infrared laser radar, energy detection and long-distance laser communication.
The invention relates to a selenium gallium lithium middle and far infrared nonlinear optical crystal, a preparation method and application thereof, wherein the selenium gallium lithium crystal is prepared according to the following chemical reaction formula:
(1)3Li+3Ga+7Se＝3LiGaSe2
(2)3Li2Se+6Ga+11Se＝6LiGaSe2
(3)6Li+3Ga2Se3+5Se＝6LiGaSe2
(4)3Li2Se+3Ga2Se3+2Se＝6LiGaSe2
the invention relates to a selenium gallium lithium middle and far infrared nonlinear optical crystal, a preparation method and application, wherein the crucible descending method used in the method for growing the selenium gallium lithium middle and far infrared nonlinear optical crystal also comprises the following post-treatment of the selenium gallium lithium nonlinear optical crystal: after the crystal growth is finished, the crystal is still left in the growth furnace for annealing, and the temperature is reduced to room temperature at the rate of 30-80 ℃/h, preferably the temperature reduction rate is 30-40 ℃/h.
Adopting high temperature melt spontaneous crystallization method or crucible descending method to obtain selenium gallium lithium middle and far infrared nonlinear optical crystal with size of 0.04 x 0.09 x 0.16 mm; by using a large-size crucible and prolonging the growth period, the selenium-gallium-lithium medium-far infrared nonlinear optical crystal with a correspondingly large size can be obtained.
According to the crystallographic data of the crystal, the crystal blank is oriented, the crystal is cut according to the required angle, thickness and section size, and the light passing surface of the crystal is polished, thus the crystal can be used as a nonlinear optical device.
The invention relates to a selenium gallium lithium middle and far infrared nonlinear optical crystal, a preparation method and application thereof.
The selenium gallium lithium mid-far infrared nonlinear optical crystal, the preparation method and the application have excellent optical performance, the infrared absorption cut-off side length is long, and the nonlinear optical coefficient is large. Has excellent nonlinear optical properties: the frequency doubling effect is of the commercial material AgGaS22 times of the total weight of the powder.
Drawings
FIG. 1 shows LiGaSe according to the invention2The crystal structure of (1);
FIG. 2 is a powder XRD pattern of the present invention;
FIG. 3 shows LiGaSe according to the present invention2The non-linear intensity of (d) and the particle size;
FIG. 4 is a calculated LiGaSe of the present invention2(ii) infrared vibration spectrum of (a);
fig. 5 is a schematic diagram of the operation of the nonlinear optical system of the present invention, in which 1 is a laser, 2 is a convex lens, 3 is a lithium gallium selenide crystal, 4 is a prism, and 5 is a filter. Laser beams emitted by a laser 1 are emitted into a selenium-gallium-lithium single crystal 3 through a convex lens 2, and the generated emergent laser beams pass through a prism 4 and a filter 5, so that the required laser beams are obtained.
Detailed Description
Any feature disclosed in this specification may, unless stated otherwise, be replaced by alternative features serving equivalent or similar purposes. Each feature is only an example of a generic series of equivalent or similar features. The description is only for the purpose of facilitating understanding of the present invention and should not be construed as specifically limiting the present invention.
The present invention is illustrated in detail by examples, but is not limited to the examples given.
Example 1
The chemical reaction formula is 3Li +3Ga +7Se ═ 3LiGaSe2Preparing selenium gallium lithium middle and far infrared nonlinear optical crystals:
the method for growing the selenium-gallium-lithium infrared nonlinear optical crystal by the high-temperature melt spontaneous crystallization method comprises the following specific operations:
a. 0.021g of Li, 0.210 g of Ga and 0.553 g of Se are weighed according to the mol ratio of 3:3:7, evenly mixed, put into a clean graphite crucible, then put into a quartz glass tube with the length of 24cm and the diameter of 12mm, and the quartz glass tube is pumped to 10 by a vacuum pump-5-10-3Carrying out melting sealing after Pa vacuum degree;
b. putting the quartz tube in the step a into a muffle furnace with program temperature control, heating to 880 ℃ at a heating rate of 30 ℃/h, and preserving heat for 50 h;
c. cooling to room temperature at a cooling rate of 3 deg.C/h to obtain a product with a size of 0.12 × 0.13 × 0.18mm3Selenium gallium lithium middle and far infrared nonlinear optical crystal.
Example 2
By the chemical reaction formula 3Li2Se+6Ga+11Se＝6LiGaSe2Preparing selenium gallium lithium middle and far infrared nonlinear optical crystals:
the method for growing the selenium-gallium-lithium infrared nonlinear optical crystal by the high-temperature melt spontaneous crystallization method comprises the following specific operations:
a. 0.279 g of Li is weighed according to the molar ratio of 3:6:112Se, 0.420 g Ga and 0.869 g Se are mixed uniformly, put into a clean graphite crucible, then put into a quartz glass tube with the length of 24cm and the diameter of 12mm, and the quartz glass tube is pumped to 10 by a vacuum pump-5-10-3Carrying out melting sealing after Pa vacuum degree;
b. b, placing the quartz tube in the step a into a muffle furnace with program temperature control, heating to 880 ℃ at a heating rate of 35 ℃/h, and preserving heat for 40 h;
c. cooling to room temperature at a cooling rate of 3 deg.C/h to obtain a product with a size of 0.16 × 0.21 × 0.24mm3Selenium gallium lithium middle and far infrared nonlinear optical crystal.
Example 3
By the chemical reaction formula 6Li +3Ga2Se3+5Se＝6LiGaSe2Preparing a selenium gallium lithium medium and far infrared nonlinear optical crystal:
the method for growing the selenium-gallium-lithium infrared nonlinear optical crystal by the high-temperature melt spontaneous crystallization method comprises the following specific operations:
a. 0.042 g of Li and 1.131 g of Ga are weighed according to the molar ratio of 6:3:52Se3Mixing with 0.395 g Se, placing into a clean graphite crucible, placing into a quartz glass tube with a length of 24cm and a diameter of 12mm, and pumping the quartz glass tube to 10mm by a vacuum pump-5-10-3Carrying out melting sealing after Pa vacuum degree;
b. putting the quartz tube in the step a into a muffle furnace with a programmed temperature control function, heating to 900 ℃ at a heating rate of 30 ℃/h, and preserving heat for 45 h;
c. cooling to room temperature at a cooling rate of 5 deg.C/h to obtain a product with a size of 0.23 × 0.31 × 0.19mm3Selenium gallium lithium middle and far infrared nonlinear optical crystal.
Example 4
By the chemical reaction formula 3Li2Se+3Ga2Se3+2Se＝6LiGaSe2Preparing selenium gallium lithium middle and far infrared nonlinear optical crystals:
the method for growing the selenium-gallium-lithium infrared nonlinear optical crystal by the high-temperature melt spontaneous crystallization method comprises the following specific operations:
a. 0.279 g of Li is weighed according to the molar ratio of 3:3:22Se, 1.131 g Ga2Se3Mixing with 0.156 g Se, placing into a clean graphite crucible, placing into a quartz glass tube with a length of 24cm and a diameter of 12mm, and pumping the quartz glass tube to 10mm by a vacuum pump-5-10-3Carrying out melting sealing after Pa vacuum degree;
b. putting the quartz tube in the step a into a muffle furnace with program temperature control, heating to 880 ℃ at a heating rate of 40 ℃/h, and preserving heat for 50 h;
c. cooling to room temperature at a cooling rate of 4 deg.C/h to obtain a product with a size of 0.6 × 0.75 × 0.16mm3Selenium gallium lithium middle and far infrared nonlinear optical crystal.
Example 5
The chemical reaction formula is 3Li +3Ga +7Se ═ 3LiGaSe2Preparing selenium gallium lithium middle and far infrared nonlinear optical crystals:
the method for growing the selenium-gallium-lithium infrared nonlinear optical crystal by the Bridgman-Stockbarge method comprises the following specific operations:
a. weighing 0.021g of Li, 0.210 g of Ga and 0.553 g of Se according to the mol ratio of 3:3:7, uniformly mixing, putting into a clean graphite crucible, then putting into a quartz glass tube with the length of 24cm and the diameter of 12mm, pumping the quartz glass tube to 10mm by a vacuum pump-5-10-3Carrying out melting sealing after Pa vacuum degree;
b. putting the quartz tube in the step a into a muffle furnace with program temperature control, heating to 880 ℃ at a heating rate of 30 ℃/h, and preserving heat for 50 h;
c, vertically descending at the speed of 0.1mm/h, carrying out selenium gallium lithium infrared nonlinear optical crystal growth in the descending process of a crystal growth device, wherein the growth period is 20 days, after the crystal growth is finished, still keeping the crystal in a growth furnace for annealing, and cooling to the room temperature at the speed of 10 ℃/h to obtain the crystal with the size of 0.13 multiplied by 0.17 multiplied by 0.22mm3Selenium gallium lithium middle and far infrared nonlinear optical crystal.
Example 6
By the chemical reaction formula 3Li2Se+6Ga+11Se＝6LiGaSe2Preparing selenium gallium lithium middle and far infrared nonlinear optical crystals:
the method for growing the selenium-gallium-lithium infrared nonlinear optical crystal by the Bridgman-Stockbarge method comprises the following specific operations:
a. 0.279 g of Li is weighed according to the molar ratio of 3:6:112Se, 0.420 g Ga and 0.869 g Se are mixed evenly and put into a clean graphite crucible, and then the graphite crucible is filled with the mixture with the length of 24cm and the diameter ofIn a 12mm quartz glass tube, the quartz tube was pumped up to 10 by means of a vacuum pump-5-10-3Carrying out melting sealing after Pa vacuum degree;
b. putting the quartz tube in the step a into a muffle furnace with program temperature control, heating to 890 ℃ at a heating rate of 20 ℃/h, and preserving heat for 40 h;
c. then vertically descending at the speed of 1mm/h, carrying out selenium gallium lithium infrared nonlinear optical crystal growth in the descending process of a crystal growth device, wherein the growth period is 10 days, after the crystal growth is finished, still keeping the crystal in a growth furnace for annealing, and cooling to room temperature at the speed of 40 ℃/h to obtain the crystal with the size of 0.17 multiplied by 0.21 multiplied by 0.33mm3Selenium gallium lithium infrared nonlinear optical crystal.
Example 7
By the chemical reaction formula 6Li +3Ga2Se3+5Se＝6LiGaSe2Preparing selenium gallium lithium middle and far infrared nonlinear optical crystals:
the method for growing the selenium-gallium-lithium infrared nonlinear optical crystal by the Bridgman-Stockbarge method comprises the following specific operations:
a. weighing 0.042 g of Li and 1.131 g of Ga according to the molar ratio of 6:3:52Se3Mixing with 0.395 g Se, placing into a clean graphite crucible, placing into a quartz glass tube with a length of 24cm and a diameter of 12mm, and pumping the quartz glass tube to 10mm by a vacuum pump-5-10-3Carrying out melting sealing after Pa vacuum degree;
b. putting the quartz tube in the step a into a muffle furnace with program temperature control, heating to 880 ℃ at a heating rate of 35 ℃/h, and preserving heat for 45 h;
c. then vertically descending at the speed of 0.5mm/h, carrying out selenium gallium lithium infrared nonlinear optical crystal growth in the descending process of a crystal growth device, wherein the growth period is 30 days, after the crystal growth is finished, still keeping the crystal in a growth furnace for annealing, and cooling to the room temperature at the speed of 50 ℃/h to obtain the crystal with the size of 0.27 multiplied by 0.33 multiplied by 0.41mm3Selenium gallium lithium middle and far infrared nonlinear optical crystal.
Example 8
By the chemical reaction formula 3Li2Se+3Ga2Se3+2Se＝6LiGaSe2Preparing selenium gallium lithium middle and far infrared nonlinear optical crystals:
the method for growing the selenium-gallium-lithium infrared nonlinear optical crystal by the Bridgman-Stockbarge method comprises the following specific operations:
a. 0.279 g of Li is weighed according to the molar ratio of 3:3:22Se, 1.131 g Ga2Se3Mixing with 0.156 g Se, placing into a clean graphite crucible, placing into a quartz glass tube with a length of 24cm and a diameter of 12mm, and pumping the quartz glass tube to 10mm by a vacuum pump-5-10-3Carrying out melting sealing after Pa vacuum degree;
b. putting the quartz tube in the step a into a muffle furnace with program temperature control, heating to 880 ℃ at a heating rate of 40 ℃/h, and preserving heat for 50 h;
c, vertically descending at the speed of 0.3mm/h, carrying out selenium-gallium-lithium infrared nonlinear optical crystal growth in the descending process of a crystal growth device, wherein the growth period is 40 days, after the crystal growth is finished, still keeping the crystal in a growth furnace for annealing, and cooling to the room temperature at the speed of 80 ℃/h to obtain the crystal with the size of 0.34 multiplied by 0.39 multiplied by 0.51mm3Selenium gallium lithium middle and far infrared nonlinear optical crystal.
Example 9
Tests show that the far infrared nonlinear optical crystals of selenium-gallium-lithium prepared in examples 1-8 belong to the tetragonal system and have the chemical formula of LiGaSe2Molecular weight of 469.16, space group of
Cell parameters of
α＝β＝γ＝90°，Z＝2，
The crystal structure is schematically shown in figure 1: in the crystal structure of the selenium gallium lithium, the valence of Li atom, Ga atom and Se atom is +1, +3 and-2 respectively; with [ LiSe ]4]And [ GaSe ]4]The tetrahedral groups are respectively connected with each other to form a zigzag chain and further connected alternately to form a chalcopyrite structure; the pure phase of the obtained lithium selenium gallium crystal was determined by powder XRD, and the result is shown in fig. 2: the figure shows that the purity of the selenium gallium lithium middle and far infrared nonlinear optical crystal powder sample is high.
Example 10
Any of the selenium-gallium-lithium medium and far infrared nonlinear optical crystals obtained in examples 1 to 8 was placed at the position 3 as shown in FIG. 5, and at room temperature, a light source of 2090nm output of a Q Ho, Tm, Cr, YAG laser was used to observe a significant 1045nm frequency doubled light output with an output intensity of AgGaS under the same conditions22 times (fig. 3), as shown in fig. 5: an infrared light beam with the wavelength of 2090nm emitted by a QHo Tm Cr YAG laser 1 is emitted into a selenium gallium lithium nonlinear optical crystal 3 through a convex lens 2 to generate frequency doubling light with the wavelength of 1045nm, an emergent light beam passing through a prism 4 contains incident light with the wavelength of 2090nm and frequency doubling light with the wavelength of 1045nm, and the incident light beam and the frequency doubling light with the wavelength of 1045nm are filtered by a filter 5 to obtain the frequency doubling light with the wavelength of 1045 nm.
The invention provides a selenium-gallium-lithium middle and far infrared nonlinear optical crystal, a preparation method and application thereof, wherein the crystal has a large nonlinear optical effect (the powder frequency doubling effect is AgGaS)22 times of that of the optical fiber) and can realize a type of phase matching (figure 3), and the transmission range covers two important atmospheric windows of 3-5 and 8-12 mu m (figure 4); the nonlinear optical crystal has potential application prospect in the technical field of middle and far infrared laser.
Claims (3)
1. The far infrared non-linear optical crystal of selenium gallium lithium is characterized in that the chemical formula of the crystal is LiGaSe2Molecular weight of 469.16, belonging to tetragonal system, space group of I
2d, unit cell parameters a = 5.843 (2) a, b = 5.843 (2) a, c = 10.614 (8) a, α = β = γ =90 °, Z = 2, V = 362.4 (4) a3The crystal structure is formed by [ LiSe4]And [ GaSe ]4]Tetrahedral elementary composition, an experiment of whichThe band gap is 1.71 eV.
2. The method for preparing the selenium gallium lithium mid-infrared nonlinear optical crystal as claimed in claim 1, characterized in that the method is prepared by a high-temperature melt spontaneous crystallization method or a Bridgman method, and the specific operation is carried out according to the following steps:
the high-temperature melt spontaneous crystallization method is used for growing the selenium gallium lithium infrared nonlinear optical crystal, and the specific operation is carried out according to the following steps:
a. li or Li as Li raw material2Ga or Ga as Se or Ga raw material2Se3Respectively and uniformly mixing with Se, putting into a clean graphite crucible, then putting into a quartz glass tube, and pumping the quartz glass tube to 10 DEG by a vacuum pump-5-10-3Carrying out melting sealing after Pa vacuum degree;
b. putting the quartz glass tube in the step a into a muffle furnace controlled by a program, heating to 880-900 ℃ within 30-50 hours, and preserving heat for 40-50 hours;
c. then slowly cooling to room temperature at the speed of 3-5 ℃/h to obtain the selenium gallium lithium middle and far infrared nonlinear optical crystal;
the method for growing the selenium-gallium-lithium infrared nonlinear optical crystal by the Bridgman-Stockbarge method comprises the following specific operations:
a. taking Li as raw material2Se; ga as the raw material is Ga or Ga2Se3(ii) a Se raw material is Se simple substance or Se-containing compound, which is uniformly mixed, put into a clean graphite crucible, then put into a quartz glass tube, and the quartz glass tube is pumped to 10 degrees by a vacuum pump-5-10-3Melting and sealing after Pa vacuum degree;
b. b, placing the sealed quartz tube in the step a into a crucible descending furnace, raising the temperature to 880-900 ℃ at the heating rate of 20-40 ℃/h, and preserving the temperature for 40-50 h;
c, vertically descending at the speed of 0.1-10mm/h, carrying out selenium gallium lithium infrared nonlinear optical crystal growth in the descending process of the crystal growth device, wherein the growth period is 10-40 days, after the crystal growth is finished, keeping the crystal in a growth furnace for annealing, and cooling to the room temperature at the speed of 10-80 ℃/h to obtain the selenium gallium lithium infrared nonlinear optical crystal.
3. The use of the selenium gallium lithium mid-far infrared nonlinear optical crystal of claim 1 in the preparation of infrared band laser frequency conversion, infrared laser guidance, infrared laser radar, energy detection, and long-distance laser communication.
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