CN103288058B - Li2In2GeSe6Nonlinear optical crystal and its preparation method and use - Google Patents
Li2In2GeSe6Nonlinear optical crystal and its preparation method and use Download PDFInfo
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- CN103288058B CN103288058B CN201210048489.0A CN201210048489A CN103288058B CN 103288058 B CN103288058 B CN 103288058B CN 201210048489 A CN201210048489 A CN 201210048489A CN 103288058 B CN103288058 B CN 103288058B
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- 239000013078 crystal Substances 0.000 title claims abstract description 96
- 230000003287 optical effect Effects 0.000 title claims abstract description 31
- 238000002360 preparation method Methods 0.000 title claims abstract description 17
- 238000000034 method Methods 0.000 claims abstract description 9
- 150000001875 compounds Chemical class 0.000 claims abstract description 5
- 238000003746 solid phase reaction Methods 0.000 claims abstract description 5
- 238000002425 crystallisation Methods 0.000 claims abstract description 4
- 230000002269 spontaneous effect Effects 0.000 claims abstract description 4
- 239000011669 selenium Substances 0.000 claims description 27
- 239000000463 material Substances 0.000 claims description 25
- 239000000126 substance Substances 0.000 claims description 15
- ZBMHAKQPBHKTCB-UHFFFAOYSA-N [Li].[In]=[Se] Chemical compound [Li].[In]=[Se] ZBMHAKQPBHKTCB-UHFFFAOYSA-N 0.000 claims description 6
- 239000000843 powder Substances 0.000 claims description 5
- 241000972773 Aulopiformes Species 0.000 claims description 4
- 230000005670 electromagnetic radiation Effects 0.000 claims description 4
- 235000019515 salmon Nutrition 0.000 claims description 4
- 238000010671 solid-state reaction Methods 0.000 claims description 4
- QIHHYQWNYKOHEV-UHFFFAOYSA-N 4-tert-butyl-3-nitrobenzoic acid Chemical compound CC(C)(C)C1=CC=C(C(O)=O)C=C1[N+]([O-])=O QIHHYQWNYKOHEV-UHFFFAOYSA-N 0.000 claims description 3
- 229910052732 germanium Inorganic materials 0.000 claims description 3
- GNPVGFCGXDBREM-UHFFFAOYSA-N germanium atom Chemical compound [Ge] GNPVGFCGXDBREM-UHFFFAOYSA-N 0.000 claims description 3
- 229910052738 indium Inorganic materials 0.000 claims description 3
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 claims description 3
- PEXNRZDEKZDXPZ-UHFFFAOYSA-N lithium selenidolithium Chemical compound [Li][Se][Li] PEXNRZDEKZDXPZ-UHFFFAOYSA-N 0.000 claims description 3
- 239000000203 mixture Substances 0.000 claims description 3
- 125000006850 spacer group Chemical group 0.000 claims description 3
- 238000010792 warming Methods 0.000 claims description 3
- 230000007423 decrease Effects 0.000 claims description 2
- 238000010438 heat treatment Methods 0.000 claims description 2
- 239000000155 melt Substances 0.000 claims description 2
- 230000005855 radiation Effects 0.000 claims description 2
- 238000003723 Smelting Methods 0.000 claims 1
- 238000004519 manufacturing process Methods 0.000 abstract description 4
- 238000005336 cracking Methods 0.000 abstract 1
- 238000003860 storage Methods 0.000 abstract 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 46
- 229910005866 GeSe Inorganic materials 0.000 description 27
- 239000000377 silicon dioxide Substances 0.000 description 22
- 238000006243 chemical reaction Methods 0.000 description 14
- 239000004570 mortar (masonry) Substances 0.000 description 12
- 238000005538 encapsulation Methods 0.000 description 10
- 238000001816 cooling Methods 0.000 description 8
- 238000002156 mixing Methods 0.000 description 8
- 239000007787 solid Substances 0.000 description 8
- 238000005245 sintering Methods 0.000 description 7
- 239000003153 chemical reaction reagent Substances 0.000 description 6
- 230000000694 effects Effects 0.000 description 4
- 238000004321 preservation Methods 0.000 description 3
- 229910019655 synthetic inorganic crystalline material Inorganic materials 0.000 description 3
- 238000010586 diagram Methods 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 208000027418 Wounds and injury Diseases 0.000 description 1
- JNDMLEXHDPKVFC-UHFFFAOYSA-N aluminum;oxygen(2-);yttrium(3+) Chemical compound [O-2].[O-2].[O-2].[Al+3].[Y+3] JNDMLEXHDPKVFC-UHFFFAOYSA-N 0.000 description 1
- 230000003321 amplification Effects 0.000 description 1
- 230000005540 biological transmission Effects 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
- 230000008025 crystallization Effects 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 230000006378 damage Effects 0.000 description 1
- 238000002050 diffraction method Methods 0.000 description 1
- 230000008030 elimination Effects 0.000 description 1
- 238000003379 elimination reaction Methods 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 208000014674 injury Diseases 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 238000003199 nucleic acid amplification method Methods 0.000 description 1
- 230000005693 optoelectronics Effects 0.000 description 1
- 230000010355 oscillation Effects 0.000 description 1
- 238000005498 polishing Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 229910052711 selenium Inorganic materials 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 238000010583 slow cooling Methods 0.000 description 1
- 238000004611 spectroscopical analysis Methods 0.000 description 1
- 229910019901 yttrium aluminum garnet Inorganic materials 0.000 description 1
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- Crystals, And After-Treatments Of Crystals (AREA)
Abstract
The invention relates to Li2In2GeSe6Compound, Li2In2GeSe6Nonlinear optical crystal and its preparation method and application; the Li2In2GeSe6The compound is prepared by adopting a solid-phase reaction; li2In2GeSe6The nonlinear optical crystal grows by adopting a high-temperature melt spontaneous crystallization method or a Bridgman method; in the presence of Li2In2GeSe6The crystal is easy to grow in the growth of the nonlinear optical crystal, is transparent and has no package, and has the advantages of high growth speed, low cost, easy obtainment of crystals with larger size and the like; obtained Li2In2GeSe6The nonlinear optical crystal has the advantages of wider light-transmitting wave band, higher hardness, good mechanical property, difficult cracking and deliquescence, easy processing and storage and the like; the Li2In2GeSe6The nonlinear optical crystal can be used for manufacturing nonlinear optical devices.
Description
Technical field
The present invention relates to a kind of Li
2in
2geSe
6compound, Li
2in
2geSe
6non-linear optic crystal (Li
2in
2geSe
6monocrystalline) and this Li
2in
2geSe
6the preparation method of monocrystalline and use Li
2in
2geSe
6the purposes of the device for non-linear optical that monocrystalline makes.
Background technology
The crystal with non-linear optical effect is called non-linear optic crystal.Here non-linear optical effect refers to the effect such as frequency multiplication and frequency, difference frequency, parameter amplification.Only have the crystal without symmetry centre just may have non-linear optical effect.Utilize the non-linear optical effect of crystal, can second harmonic generator be made, upper and lower frequency converter, the device for non-linear optical such as optical parametric oscillator.The laser that laser apparatus produces carries out frequency inverted by device for non-linear optical, thus obtains the laser of more how useful wavelength, and laser apparatus is more widely used.According to the difference of materials application wave band, ultraviolet region, visible and near-infrared region and mid-infrared light district nonlinear optical material three major types can be divided into.The non-linear optical crystal material of visible region and ultraviolet region can meet the requirement of practical application; KTP (KTiOPO is mainly contained as practical in two frequencys multiplication (532nm) crystal
4), BBO (β-BaB
2o
4), LBO (LiB
3o
5) crystal; In frequency tripling (355nm) crystal, practicality has BBO, LBO, CBO (CsB
3o
5) available.And the nonlinear crystal development of infrared band is slow; The material in infrared light district is ABC mostly
2the chalcopyrite structure semiconductor material of type, as AgGaQ
2(Q=S, Se, Te), the light injury threshold of infrared non-linear crystal is too low and crystal growth difficult, directly affects actual use.Middle-infrared band non-linear optic crystal has important application at optoelectronic areas, and such as the laser (as 1.064 μm) of near-infrared band can be extended to middle infrared by the means such as optical parametric oscillation or optically erasing by it; Also can to the important laser in mid-infrared light district (as CO
2laser, 10.6 μm) carry out frequency multiplication, this is significant for the continuously adjustable laser of acquisition wavelength.Therefore the novel infrared nonlinear optical crystal material finding premium properties has become one of the difficult point and direction, forward position of current nonlinear optical material research field.
Summary of the invention
The object of the invention is to provide a kind of chemical formula to be Li
2in
2geSe
6compound.
Another object of the present invention is to provide a kind of Li
2in
2geSe
6non-linear optic crystal.
Still a further object of the present invention is to provide Li
2in
2geSe
6the preparation method of non-linear optic crystal.
A further object of the invention is to provide Li
2in
2geSe
6the purposes of non-linear optic crystal.
Technical scheme of the present invention is as follows:
The invention provides a kind of chemical formula is Li
2in
2geSe
6compound.
Li provided by the invention
2in
2geSe
6the preparation method of compound, its step is as follows:
By containing Li material, containing In material, to prepare burden according to the ratio of mol ratio Li:In:Ge:Se=2:2:1:6 containing Ge material and Se and after mixing, be heated to 700-800 DEG C carry out solid state reaction and (in principle, adopt general chemical synthesis process to prepare Li
2in
2geSe
6compound; The preferred solid reaction process of the present invention), obtaining chemical formula is Li
2in
2geSe
6compound; Described is lithium selenide or selenium indium lithium containing Li material; Described is germanium simple substance or two Germanium selenide containing Ge material; Described is indium simple substance or three selenizing two indiums or selenium indium lithium containing In material.
The step that solid state reaction is carried out in described heating is: by loading in silica tube after above-mentioned batching grinding, be evacuated to 10 to silica tube
-3pa also carries out fusing encapsulation, and put into retort furnace, with the ramp of 10-50 DEG C/h to 700-800 DEG C, constant temperature 48-72 hour, takes out sample after cooling; The sample taken out is reground and is placed in silica tube again and is evacuated to 10
-3pa also carries out fusing encapsulation, then puts into retort furnace and be warming up to 700-800 DEG C of sintering 48 hours; Sample is taken out, and smashs to pieces and grind to obtain Powdered Li
2in
2geSe
6compound.
Described Li
2in
2geSe
6compound can be prepared by following chemical equation:
(1)Li
2Se+In
2Se
3+GeSe
2＝Li
2In
2GeSe
6；
(2)Li
2Se+2In+Ge+5Se＝Li
2In
2GeSe
6；
(3)Li
2Se+In
2Se
3+Ge+2Se＝Li
2In
2GeSe
6；
(4)Li
2Se+2In+3Se+GeSe
2＝Li
2In
2GeSe
6；
(5)2LiInSe
2+GeSe
2＝Li
2In
2GeSe
6；
(6)2LiInSe
2+Ge+2Se＝Li
2In
2GeSe
6。
Li provided by the invention
2in
2geSe
6non-linear optic crystal does not have symmetry centre, and belong to oblique system, spacer is Cc, and its unit cell parameters is:
β=109.83 °.
Li provided by the invention
2in
2geSe
6the preparation method of non-linear optic crystal, it is high-temperature fusant spontaneous crystallization method growth Li
2in
2geSe
6non-linear optic crystal, the steps include: Powdered Li
2in
2geSe
6compound is heated to melt to obtain high temperature solution after keeping 24-96 hour, be cooled to room temperature with the rate of temperature fall of 1-10 DEG C/h, obtains the Li of transparent salmon
2in
2geSe
6crystal.
Described Powdered Li
2in
2geSe
6being prepared as follows of compound:
By containing Li material, containing In material, to prepare burden according to the ratio of mol ratio Li:In:Ge:Se=2:2:1:6 containing Ge material and simple substance Se and after mixing, be heated to 700-800 DEG C carry out solid state reaction and (in principle, adopt general chemical synthesis process to prepare Li
2in
2geSe
6compound; The preferred solid reaction process of the present invention), obtaining chemical formula is Li
2in
2geSe
6compound; Described is lithium selenide or selenium indium lithium containing Li material; Described is germanium simple substance or two Germanium selenide containing Ge material; Described is indium simple substance or three selenizing two indiums or selenium indium lithium containing In material.
Described Li
2in
2geSe
6compound can be prepared by following chemical equation:
(1)Li
2Se+In
2Se
3+GeSe
2＝Li
2In
2GeSe
6；
(2)Li
2Se+2In+Ge+5Se＝Li
2In
2GeSe
6；
(3)Li
2Se+In
2Se
3+Ge+2Se＝Li
2In
2GeSe
6；
(4)Li
2Se+2In+3Se+GeSe
2＝Li
2In
2GeSe
6；
(5)2LiInSe
2+GeSe
2＝Li
2In
2GeSe
6；
(6)2LiInSe
2+Ge+2Se＝Li
2In
2GeSe
6。
Li provided by the invention
2in
2geSe
6a preparation method again of non-linear optic crystal, it is Bridgman-Stockbarge method for growing Li
2in
2geSe
6non-linear optic crystal, its step is as follows:
By Powdered Li
2in
2geSe
6compound puts into crystal growing apparatus, and be slowly warming up to its fusing, after it melts completely, crystal growing apparatus vertically declines with the speed of 0.1-10mm/h, in crystal growing apparatus decline process, carry out Li
2in
2geSe
6non-linear optic crystal grows, and its growth cycle is 5-20 days;
Bridgman-Stockbarge method for growing Li of the present invention
2in
2geSe
6non-linear optic crystal also comprises Li
2in
2geSe
6the aftertreatment of non-linear optic crystal: after crystal growth terminates, will stay in growth furnace and anneals by crystal, be cooled to room temperature (preferred rate of temperature fall 20 ~ 50 DEG C/h) with the speed of 20 ~ 100 DEG C/h.
Adopt above-mentioned two kinds of methods all can obtain the Li being of a size of centimetre-sized
2in
2geSe
6non-linear optic crystal; Use large size crucible, and extend vegetative period, then can obtain corresponding large-size Li
2in
2geSe
6non-linear optic crystal.
According to the crystallography data of crystal, crystal boule is directed, by required angle, thickness and sectional dimension sliced crystal, crystal is led to light mirror polish, namely can be used as device for non-linear optical and use, this Li
2in
2geSe
6non-linear optic crystal has physical and chemical performance and stablizes, and hardness is comparatively large, and good mechanical property is not easily broken, not easily deliquescence, is easy to the advantages such as processing and preservation; So the present invention also provides Li further
2in
2geSe
6the purposes of non-linear optic crystal, this Li
2in
2geSe
6non-linear optic crystal is for the preparation of device for non-linear optical, and this device for non-linear optical comprises at least a branch of incidence electromagnetic radiation by least one piece of Li
2in
2geSe
6the device that at least a branch of frequency is different from the output radiation of incidence electromagnetic radiation is produced after non-linear optic crystal.
Li of the present invention
2in
2geSe
6compound, this compound non-linear optic crystal and its production and use there is following effect:
At this Li
2in
2geSe
6the growing crystals of non-linear optic crystal is easily grown up and the transparent advantages such as have the speed of growth very fast, cost is low without wrapping up, easy acquisition large-size crystal; The Li obtained
2in
2geSe
6non-linear optic crystal has wider transmission region, and hardness is comparatively large, good mechanical property, and not easily broken and deliquescence is easy to the advantages such as processing and preservation; This Li
2in
2geSe
6non-linear optic crystal can be used for making device for non-linear optical.
Accompanying drawing explanation
Fig. 1 adopts Li of the present invention
2in
2geSe
6the fundamental diagram of a kind of typical device for non-linear optical that non-linear optic crystal is made, wherein 1 is laser apparatus, and 2 is incoming laser beams, and 3 is the Li after crystal aftertreatment and optical manufacturing
2in
2geSe
6non-linear optic crystal, 4 is produced outgoing laser beams, and 5 is filter plates.
Fig. 2 is Li
2in
2geSe
6the structural representation of non-linear optic crystal.
Embodiment
Embodiment 1, prepares Powdered Li
2in
2geSe
6compound:
Adopt (1) Li
2se+In
2se
3+ GeSe
2=Li
2in
2geSe
6reaction formula solid reaction process prepares Li
2in
2geSe
6compound; Described Li
2se is 1.857 grams, described In
2se
3be 9.330 grams, described GeSe
2it is 4.611 grams; I.e. Li
2se:In
2se
3: GeSe
2=0.02mol:0.02mol:0.02mol;
Concrete operation step is, takes reagent respectively, they are put into mortar in glove box by above-mentioned dosage, and mixing is also carefully ground, and then loads in the silica tube of Φ 12mm × 16mm, is evacuated to 10
-3with oxyhydrogen flame, silica tube fusing is encapsulated after pa, put into retort furnace, slowly rise to 800 DEG C, constant temperature 48-72 hour, takes out after cooling, takes out sample and is reground, be placed in silica tube again and vacuumize encapsulation, in 800 DEG C of sintering 48 hours in retort furnace, taken out, put into mortar and smash to pieces and grind to obtain Powdered Li
2in
2geSe
6compound.
Embodiment 2, prepares Powdered Li
2in
2geSe
6compound:
Adopt Li
2se+2In+Ge+5Se=Li
2in
2geSe
6reaction formula solid reaction process prepares Li
2in
2geSe
6compound; Described Li
2se is 1.857 grams, and described In is 4.593 grams, and described Ge is 1.452 grams, and described Se is 7.896 grams, i.e. Li
2se:In:Ge:Se=0.02mol:0.04mol:0.02mol:0.10mol;
Its concrete operation step is, takes reagent respectively, they are put into mortar in glove box by above-mentioned dosage, and mixing is also carefully ground, and then loads in the silica tube of Φ 12mm × 16mm, is evacuated to 10
-3with flame, silica tube fusing is encapsulated after pa, put into retort furnace, slowly rise to 800 DEG C, its temperature rise rate is 10 DEG C/h, constant temperature 48 hours, take out after cooling, taking-up sample is reground, then is placed in silica tube and vacuumizes encapsulation, in 800 DEG C of sintering 48 hours in retort furnace, taken out, put into mortar smash to pieces grind to obtain preparation Powdered Li
2in
2geSe
6compound.
Embodiment 3, prepares Powdered Li
2in
2geSe
6compound:
Adopt Li
2se+In
2se
3+ Ge+2Se=Li
2in
2geSe
6reaction formula solid reaction process prepares Li
2in
2geSe
6compound; Described Li
2se is 1.857 grams, described In
2se
3be 9.330 grams, described Ge is 1.452 grams, and described Se is 3.158 grams, i.e. Li
2se:In
2se
3: Ge:Se=0.02mol:0.02mol:0.02mol:0.04mol;
Concrete operation step is, concrete operation step is, takes reagent respectively, they are put into mortar in glove box by above-mentioned dosage, and mixing is also carefully ground, and then loads in the silica tube of Φ 12mm × 16mm, is evacuated to 10
-3with flame, silica tube fusing is encapsulated after pa, put into retort furnace, slowly rise to 800 DEG C, its temperature rise rate is 30 DEG C/h, constant temperature 72 hours, take out after cooling, taking-up sample is reground, then is placed in silica tube and vacuumizes encapsulation, in 800 DEG C of sintering 48 hours in retort furnace, taken out, put into mortar and smash to pieces and grind to obtain Powdered Li
2in
2geSe
6compound.
Embodiment 4, prepares Powdered Li
2in
2geSe
6compound:
Adopt Li
2se+2In+3Se+GeSe
2=Li
2in
2geSe
6reaction formula solid reaction process prepares Li
2in
2geSe
6compound; Described Li
2se is 1.857 grams, and described In is 4.593 grams, and described Se is 4.738 grams, described GeSe
2be 4.611 grams, i.e. Li
2se:In:Se:GeSe
2=0.02mol:0.04mol:0.06mol:0.02mol;
Its concrete operation step is, takes reagent respectively, they are put into mortar in glove box by above-mentioned dosage, and mixing is also carefully ground, and then loads in the silica tube of Φ 12mm × 16mm, is evacuated to 10
-3with flame, silica tube fusing is encapsulated after pa, put into retort furnace, slowly rise to 800 DEG C, its temperature rise rate is 10 DEG C/h, constant temperature 48 hours, take out after cooling, taking-up sample is reground, then is placed in silica tube and vacuumizes encapsulation, in 800 DEG C of sintering 48 hours in retort furnace, taken out, put into mortar smash to pieces grind to obtain preparation Powdered Li
2in
2geSe
6compound.
Embodiment 5, prepares Powdered Li
2in
2geSe
6compound:
Adopt 2LiInSe
2+ GeSe
2=Li
2in
2geSe
6reaction formula solid reaction process prepares Li
2in
2geSe
6compound; Described LiInSe
2be 11.187 grams, described GeSe
2be 4.611 grams, i.e. LiInSe
2: GeSe
2=0.04mol:0.02mol;
Its concrete operation step is, takes reagent respectively, they are put into mortar in glove box by above-mentioned dosage, and mixing is also carefully ground, and then loads in the silica tube of Φ 12mm × 16mm, is evacuated to 10
-3with flame, silica tube fusing is encapsulated after pa, put into retort furnace, slowly rise to 800 DEG C, its temperature rise rate is 30 DEG C/h, constant temperature 48 hours, take out after cooling, taking-up sample is reground, then is placed in silica tube and vacuumizes encapsulation, in 800 DEG C of sintering 48 hours in retort furnace, taken out, put into mortar smash to pieces grind to obtain preparation Powdered Li
2in
2geSe
6compound products.
Embodiment 6, prepares Powdered Li
2in
2geSe
6compound:
Adopt 2LiInSe
2+ Ge+2Se=Li
2in
2geSe
6reaction formula solid reaction process prepares Li
2in
2geSe
6compound; Described LiInSe
2be 11.187 grams, described Ge is 1.452 grams, and described Se is 3.158 grams, i.e. LiInSe
2: Ge:Se=0.04mol:0.02mol:0.04mol;
Its concrete operation step is, takes reagent respectively, they are put into mortar in glove box by above-mentioned dosage, and mixing is also carefully ground, and then loads in the silica tube of Φ 12mm × 16mm, is evacuated to 10
-3with flame, silica tube fusing is encapsulated after pa, put into retort furnace, slowly rise to 800 DEG C, its temperature rise rate is 10 DEG C/h, constant temperature 48 hours, take out after cooling, taking-up sample is reground, then is placed in silica tube and vacuumizes encapsulation, in 800 DEG C of sintering 48 hours in retort furnace, taken out, put into mortar smash to pieces grind to obtain preparation Powdered Li
2in
2geSe
6compound.
Embodiment 7, adopts high-temperature fusant spontaneous crystallization legal system for Li
2in
2geSe
6crystal:
By the Li obtained in embodiment 1 to 6
2in
2geSe
6powder loads in the quartz glass tube of Φ 12mm × 16mm, is evacuated to 10
-3after handkerchief, be placed in tubular type growth furnace with oxyhydrogen flame encapsulation, slowly rise to 900 DEG C, constant temperature 72 hours, with the speed slow cooling of 5 DEG C/h to room temperature, close tubular type growth furnace; Cut after silica tube cooling, the Li of transparent salmon can be obtained
2in
2geSe
6crystal.
Embodiment 8, adopts falling crucible method to prepare Li
2in
2geSe
6crystal:
By the Li obtained in embodiment 1 to 6
2in
2geSe
6powder loads in the quartz glass tube of Φ 12mm × 16mm, is evacuated to 10
-3after handkerchief, with oxyhydrogen flame encapsulation be placed in crystal growing furnace, slowly rise to 900 DEG C raw material is melted completely after, growing apparatus vertically declines with the speed of 0.1-10mm/ hour; After crystal growth terminates, growing apparatus was down to room temperature with 30 hours, obtained the Li of transparent salmon
2in
2geSe
6crystal.
After tested, the Li prepared by above-described embodiment 7-8
2in
2geSe
6non-linear optic crystal belongs to oblique system, and spacer is Cc, and its unit cell parameters is:
β=109.83 °, Z=4,
there is frequency-doubled effect; Fig. 2 is this Li
2in
2geSe
6the structural representation of non-linear optic crystal.
Embodiment 9:
By the Li of embodiment 7 and 8 gained
2in
2geSe
6crystal is done through spectrometry, and this crystal is transparent within the scope of 0.54 μm of-18 mum wavelength; Not easily broken, be easy to cutting, polishing and preservation, not deliquescence; By the Li of embodiment 7,8 gained
2in
2geSe
6crystal, being placed on accompanying drawing 1 shown device label is the position of 3, and at room temperature, with tune Q Ho:YAG laser light source, incident wavelength is the infrared light of 2090nm, and output wavelength is the frequency doubled light of 1045nm, laser intensity and AgGaSe
2quite.
Accompanying drawing 1 adopts Li of the present invention
2in
2geSe
6the fundamental diagram of a kind of typical device for non-linear optical that non-linear optic crystal is made, wherein 1 is laser apparatus, and 2 is incoming laser beams, and 3 is the Li after crystal aftertreatment and optical manufacturing
2in
2geSe
6non-linear optic crystal, 4 is produced outgoing laser beams, and 5 is filter plates; Send incoming laser beam 2 by laser apparatus 1 and inject Li
2in
2geSe
6single crystal 3, the outgoing laser beam 4 produced is by filter plate 5, and the laser beam required for obtaining;
Use Li of the present invention
2in
2geSe
6the device that non-linear optic crystal makes can be a times frequency generator, upper and lower frequency converter, optical parametric oscillator etc.Laser apparatus 1 can be mix ream yttrium aluminum garnet (Ho:YAG) laser apparatus or other laser apparatus, and concerning the frequency doubling device using Ho:YAG laser light source, the infrared light of incoming beam 2 to be wavelength be 2090nm, passes through Li
2in
2geSe
6it is the frequency doubled light of 1045 that non-linear optic crystal produces wavelength, and outgoing beam 4 is the fundamental frequency light of 2090nm and the frequency doubled light of 1045nm containing wavelength, and the effect of filter plate 5 is elimination fundamental frequency light compositions, only allows frequency doubled light to pass through.
Claims (6)
1. a Li
2in
2geSe
6non-linear optic crystal, this Li
2in
2geSe
6non-linear optic crystal does not have symmetry centre, and belong to oblique system, spacer is Cc, and its unit cell parameters is: a=12.7226 (4)
b=7.4527 (4)
c=12.6698 (5)
β=109.83 °.
2. Li described in a claim 1
2in
2geSe
6the preparation method of non-linear optic crystal, it is high-temperature fusant spontaneous crystallization method growth Li
2in
2geSe
6non-linear optic crystal, the steps include: Powdered Li
2in
2geSe
6compound is heated to melt to obtain high temperature solution after keeping 24-96 hour, be cooled to room temperature with the rate of temperature fall of 1-10 DEG C/h, obtains the Li of transparent salmon
2in
2geSe
6crystal.
3. by Li described in claim 2
2in
2geSe
6the preparation method of non-linear optic crystal, is characterized in that, described Powdered Li
2in
2geSe
6being prepared as follows of compound:
By containing Li material, containing In material, mix according to the ratio of mol ratio Li:In:Ge:Se=2:2:1:6 containing Ge material and Se after, heating carry out solid state reaction, obtaining chemical formula is Li
2in
2geSe
6compound, grind to obtain Powdered Li through smashing to pieces
2in
2geSe
6compound; Described is lithium selenide or selenium indium lithium containing Li material; Described is germanium simple substance or two Germanium selenide containing Ge material; Described is indium simple substance or three selenizing two indiums or selenium indium lithium containing In material.
4. Li described in a claim 1
2in
2geSe
6the preparation method of non-linear optic crystal, it is Bridgman-Stockbarge method for growing Li
2in
2geSe
6non-linear optic crystal, its step is as follows:
By Li
2in
2geSe
6powder puts into crystal growing apparatus, is slowly warming up to powder smelting, and after powder melts completely, crystal growing apparatus vertically declines with the speed of 0.1-10mm/h, in crystal growing apparatus decline process, carry out Li
2in
2geSe
6non-linear optic crystal grows, and its growth cycle is 5-20 days.
5. by Li described in claim 4
2in
2geSe
6the preparation method of non-linear optic crystal, is characterized in that, also comprises Li
2in
2geSe
6the aftertreatment of non-linear optic crystal: after crystal growth terminates, will stay in growth furnace and anneals by crystal, be cooled to room temperature with the speed of 20 ~ 50 DEG C/h.
6. a Li according to claim 1
2in
2geSe
6the purposes of non-linear optic crystal, is characterized in that, this Li
2in
2geSe
6non-linear optic crystal is for the preparation of device for non-linear optical, and prepared device for non-linear optical comprises at least a branch of incidence electromagnetic radiation by least one piece of Li
2in
2geSe
6the device that at least a branch of frequency is different from the output radiation of incidence electromagnetic radiation is produced after non-linear optic crystal.
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| CN103866391B (en) * | 2014-03-21 | 2018-07-20 | 中国科学院福建物质结构研究所 | Infrared non-linear optics powder and monocrystal selenium germanium gallium lead |
| CN104649271A (en) * | 2015-02-05 | 2015-05-27 | 上海工程技术大学 | KYSiS4 compound, KYSiS4 nonlinear optical crystal, preparation method and application |
| CN105350082B (en) * | 2015-11-18 | 2018-07-03 | 中国科学院理化技术研究所 | Na2In2GeSe6Nonlinear optical crystal and its preparation method and use |
| CN105803531B (en) * | 2016-04-13 | 2017-12-29 | 浙江大学 | Quaternary selenide nonlinear optical crystal and preparation method thereof and its purposes |
| CN108585483B (en) * | 2018-06-22 | 2021-04-27 | 武汉理工大学 | Melting process of germanium-based infrared chalcogenide glass |
| CN110699755B (en) * | 2018-07-10 | 2022-04-05 | 天津大学 | Method for preparing two-dimensional layered material by stripping ternary atomic crystal |
| CN109610002A (en) * | 2018-11-29 | 2019-04-12 | 中国科学院理化技术研究所 | Inorganic compound, its purposes and preparation as non-linear optical crystal material |
| CN110808407B (en) * | 2019-11-01 | 2020-11-20 | 宁德新能源科技有限公司 | Phosphorus-free sulfide solid electrolyte |
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| Title |
|---|
| Characterization of New Infrared Nonlinear Optical Material with High Laser Damage Threshold, Li2Ga2GeS6;Youngsik Kim et al.;《Chem. Mater.》;20080821;第20卷(第19期);第6049页"Experimental Section"部分 * |
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