CN103290480A - Li2In2SiS6 compound and Li2In2GSiS6 nonlinear optical crystal as well as preparation methods and applications thereof - Google Patents

Li2In2SiS6 compound and Li2In2GSiS6 nonlinear optical crystal as well as preparation methods and applications thereof Download PDF

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CN103290480A
CN103290480A CN2012100484867A CN201210048486A CN103290480A CN 103290480 A CN103290480 A CN 103290480A CN 2012100484867 A CN2012100484867 A CN 2012100484867A CN 201210048486 A CN201210048486 A CN 201210048486A CN 103290480 A CN103290480 A CN 103290480A
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姚吉勇
尹文龙
冯凯
郝文钰
傅佩珍
吴以成
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Technical Institute of Physics and Chemistry of CAS
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Abstract

The invention relates to a Li2In2SiS6 compound and a Li2In2SiS6 nonlinear optical crystal as well as preparation methods and applications thereof. The Li2In2SiS6 compound is prepared by performing a solid-phase reaction; the Li2In2SiS6 nonlinear optical crystal is prepared in a high-temperature melt growth manner by using a spontaneous crystallization method or a bridgman-stockbarger method; during the growth of the Li2In2SiS6 nonlinear optical crystal, the crystal is easy to grow up, transparent and not wrapped, so that the method has the advantages of rapid growth speed, low cost, easy obtainment of the large-size crystal and the like. The obtained Li2In2SiS6 nonlinear optical crystal has the advantages of being wide in light-pervious waveband, large in hardness, good in mechanical property, difficult to break and deliquesce, easy to machine and store and the like. Thus, the Li2In2SiS6 nonlinear optical crystal can be used for manufacturing a nonlinear optical component.

Description

Li 2In 2SiS 6Compound, Li 2In 2SiS 6Non-linear optic crystal and method for making and purposes
Technical field
The present invention relates to a kind of Li 2In 2SiS 6Compound, Li 2In 2SiS 6Non-linear optic crystal (Li 2In 2SiS 6Monocrystalline) and this Li 2In 2SiS 6The preparation method of monocrystalline and use Li 2In 2SiS 6The purposes of the device for non-linear optical that monocrystalline is made.
Background technology
Crystal with non-linear optical effect is called non-linear optic crystal.Here non-linear optical effect refers to effects such as frequency multiplication and frequency, difference frequency, parameter amplification.Have only the crystal with symmetry centre just non-linear optical effect may be arranged.Utilize the non-linear optical effect of crystal, can make second harmonic generator, upper and lower frequency converter, device for non-linear optical such as optical parametric oscillator.The laser that laser apparatus produces can carry out frequency inverted by device for non-linear optical, thereby obtains the laser of how useful wavelength, and laser apparatus is more widely used.According to the difference of material application band, can be divided into ultraviolet region, visible and near-infrared region and mid-infrared light district nonlinear optical material three major types.The non-linear optical crystal material of visible region and ultraviolet region can satisfy requirement of actual application; As the practical KTP (KTiOPO that mainly contains in two frequencys multiplication (532nm) crystal 4), BBO (β-BaB 2O 4), LBO (LiB 3O 5) crystal; Practical in frequency tripling (355nm) crystal have BBO, LBO, a CBO (CsB 3O 5) available.And the development of the nonlinear crystal of infrared band is slow; The material in infrared light district is ABC mostly 2The chalcopyrite structure semiconductor material of type is as AgGaQ 2(Te), the too low and crystal growth difficulty of the light injury threshold of infrared non-linear crystal has directly influenced actual use for Q=S, Se.The middle-infrared band non-linear optic crystal has important use at optoelectronic areas, and for example it can extend to middle infrared with the laser (as 1.064 μ m) of near-infrared band by means such as optical parametric oscillation or optical parameter amplifications; Also can be to the important laser in mid-infrared light district (as CO 2Laser, 10.6 μ m) carry out frequency multiplication, this is significant for obtaining the continuously adjustable laser of wavelength.Therefore the novel infrared nonlinear optical crystal material of seeking premium properties has become one of the difficult point of current nonlinear optical material research field and forward position direction.
Summary of the invention
It is Li that the object of the invention is to provide a kind of chemical formula 2In 2SiS 6Compound.
Another purpose of the present invention is to provide a kind of Li 2In 2SiS 6Non-linear optic crystal.
Still a further object of the present invention is to provide Li 2In 2SiS 6The preparation method of non-linear optic crystal.
A further object of the invention is to provide Li 2In 2SiS 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 2SiS 6Compound.
Li provided by the invention 2In 2SiS 6The preparation method of compound, its step is as follows:
To contain the Li material, contain the In material, contain Si material and S according to mol ratio Li: In: Si: S=2: 2: 1: 6 ratio batching and mix after, be heated to 800-900 ℃ and carry out solid state reaction and (in principle, adopt general chemical synthesis process can prepare Li 2In 2SiS 6Compound; The preferred solid reaction process of the present invention), obtaining chemical formula is Li 2In 2SiS 6Compound; The described Li of containing material is lithium sulfide or sulphur indium lithium; The described Si of containing material is elementary silicon or silicon disulfide; The described In of containing material is indium simple substance or indium trisulfide or sulphur indium lithium.
The step that solid state reaction is carried out in described heating is: pack into after above-mentioned batching is ground in the silica tube, silica tube is evacuated to 10 -3Pa also melts encapsulation, puts into retort furnace, is warming up to 800-900 ℃ with 10-50 ℃/hour speed, constant temperature 48-72 hour, takes out sample after cooling; The sample that takes out is ground mixing again places silica tube to be evacuated to 10 again -3Pa also melts encapsulation, puts into retort furnace again and is warming up to 800-900 ℃ of sintering 48 hours; Sample is taken out, and smash to pieces grind Powdered Li 2In 2SiS 6Compound.
Described Li 2In 2SiS 6Compound can prepare by following chemical equation:
(1)Li 2S+In 2S 3+SiS 2＝Li 2In 2SiS 6；
(2)Li 2S+2In+Si+5S＝Li 2In 2SiS 6；
(3)Li 2S+In 2S 3+Si+2S＝Li 2In 2SiS 6；
(4)Li 2S+2In+3S+SiS 2＝Li 2In 2SiS 6；
(5)2LiInS 2+SiS 2＝Li 2In 2SiS 6；
(6)2LiInS 2+Si+2S＝Li 2In 2SiS 6。
Li provided by the invention 2In 2SiS 6Non-linear optic crystal does not possess symmetry centre, belongs to oblique system, and spacer is Cc, and its unit cell parameters is:
Figure BDA0000138595370000021
β=110.06 °.
Li provided by the invention 2In 2SiS 6The preparation method of non-linear optic crystal, it is high-temperature fusant spontaneous crystallization method growth Li 2In 2SiS 6Non-linear optic crystal the steps include: Powdered Li 2In 2SiS 6Compound be heated to melt high temperature solution and keep 24-96 hour after, be cooled to room temperature with 1-10 ℃/hour rate of temperature fall, obtain faint yellow transparent Li 2In 2SiS 6Crystal.
Described Powdered Li 2In 2SiS 6Being prepared as follows of compound:
To contain the Li material, contain the In material, contain Si material and simple substance S according to mol ratio Li: In: Si: S=2: 2: 1: 6 ratio batching and mix after, being heated to 800-900 ℃ carries out solid state reaction and (in principle, adopts general chemical synthesis process can prepare Li 2In 2SiS 6Compound; The preferred solid reaction process of the present invention), obtaining chemical formula is Li 2In 2SiS 6Compound; The described Li of containing material is lithium sulfide or sulphur indium lithium; The described Si of containing material is elementary silicon or silicon disulfide; The described In of containing material is indium simple substance or indium trisulfide or sulphur indium lithium.
Described Li 2In 2SiS 6Compound can prepare by following chemical equation:
(1)Li 2S+In 2S 3+SiS 2＝Li 2In 2SiS 6；
(2)Li 2S+2In+Si+5S＝Li 2In 2SiS 6；
(3)Li 2S+In 2S 3+Si+2S＝Li 2In 2SiS 6；
(4)Li 2S+2In+3S+SiS 2＝Li 2In 2SiS 6；
(5)2LiInS 2+SiS 2＝Li 2In 2SiS 6；
(6)2LiInS 2+Si+2S＝Li 2In 2SiS 6。
Li provided by the invention 2In 2SiS 6A preparation method again of non-linear optic crystal, it is Bridgman-Stockbarge method for growing Li 2In 2SiS 6Non-linear optic crystal, its step is as follows:
With Powdered Li 2In 2SiS 6Compound is put into crystal growing apparatus, slowly is warming up to its fusing, treat that it melts fully after, crystal growing apparatus vertically descends with the speed of 0.1-10mm/h, carries out Li in crystal growing apparatus decline process 2In 2SiS 6The non-linear optic crystal growth, its growth cycle is 5-20 days;
Bridgman-Stockbarge method for growing Li of the present invention 2In 2SiS 6Non-linear optic crystal also comprises Li 2In 2SiS 6The aftertreatment of non-linear optic crystal: after crystal growth finishes, will crystal stay in the growth furnace and anneal, be cooled to room temperature (20～50 ℃/hour of preferred rate of temperature fall) with 20～100 ℃/hour speed.
Adopt above-mentioned two kinds of methods all can obtain to be of a size of the Li of centimetre-sized 2In 2SiS 6Non-linear optic crystal; Use the large size crucible, and prolong vegetative period, then can obtain corresponding large-size Li 2In 2SiS 6Non-linear optic crystal.
According to the crystallography data of crystal, with crystal blank orientation, by required angle, thickness and sectional dimension sliced crystal, with the logical light mirror polish of crystal, namely can be used as device for non-linear optical and use this Li 2In 2SiS 6Non-linear optic crystal has physical and chemical performance to be stablized, and hardness is bigger, and good mechanical property is not easily broken, is difficult for deliquescence, is easy to advantages such as processing and preservation; So the present invention also further provides Li 2In 2SiS 6The purposes of non-linear optic crystal, this Li 2In 2SiS 6Non-linear optic crystal is for the preparation of device for non-linear optical, and this device for non-linear optical comprises a branch of at least incidence electromagnetic radiation by at least one Li 2In 2SiS 6Produce the device that a branch of at least frequency is different from the output radiation of incidence electromagnetic radiation behind the non-linear optic crystal.
Li of the present invention 2In 2SiS 6Compound, the non-linear optic crystal of this compound and its production and use have following effect:
At this Li 2In 2SiS 6The growing crystals of non-linear optic crystal is easily grown up and transparent nothing parcel, and it is very fast to have the speed of growth, and cost is low, obtains advantages such as large-size crystal easily; The Li that obtains 2In 2SiS 6Non-linear optic crystal has wideer transmission region, and hardness is bigger, good mechanical property, and not easily broken and deliquescence is easy to advantages such as processing and preservation; This Li 2In 2SiS 6Non-linear optic crystal can be used for making device for non-linear optical.
Description of drawings
Fig. 1 adopts Li of the present invention 2In 2SiS 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, the 2nd, incoming laser beam, the 3rd, the Li after crystal aftertreatment and optics processing 2In 2SiS 6Non-linear optic crystal, the 4th, the outgoing laser beam that produces, the 5th, filter plate.
Fig. 2 is Li 2In 2SiS 6The structural representation of non-linear optic crystal.
Embodiment
Embodiment 1, prepares Powdered Li 2In 2SiS 6Compound:
Adopt (1) Li 2S+In 2S 3+ SiS 2=Li 2In 2SiS 6Reaction formula prepares Li with solid reaction process 2In 2SiS 6Compound; Described Li 2S is 1.379 grams, described In 2S 3Be 9.775 grams, described SiS 2Be 2.767 grams; Be Li 2S: In 2S 3: SiS 2=0.03mol: 0.03mol: 0.03mol;
The concrete operations step is, takes by weighing reagent respectively by above-mentioned dosage in glove box, and they are put into mortar, mixes and careful the grinding, in the silica tube of the Φ 12mm * 16mm that packs into then, is evacuated to 10 -3With oxyhydrogen flame the silica tube fusing is encapsulated behind the pa, put into retort furnace, slowly rise to 800 ℃, constant temperature 48-72 hour, take out after cooling, take out sample and grind mixing again, place silica tube to vacuumize encapsulation again, in retort furnace in 800 ℃ of sintering 48 hours, with its taking-up, put into mortar smash to pieces grind Powdered Li 2In 2SiS 6Compound.
Embodiment 2, prepare Powdered Li 2In 2SiS 6Compound:
Adopt Li 2S+2In+Si+5S=Li 2In 2SiS 6Reaction formula prepares Li with solid reaction process 2In 2SiS 6Compound; Described Li 2S is 1.379 grams, and described In is 6.889 grams, and described Si is 0.843 gram, and described S is 4.811 gram, i.e. Li 2S: In: Si: S=0.03mol: 0.06mol: 0.03mol: 0.15mol;
Its concrete operations step is, takes by weighing reagent respectively by above-mentioned dosage in glove box, and they are put into mortar, mixes and careful the grinding, in the silica tube of the Φ 12mm * 16mm that packs into then, is evacuated to 10 -3With flame the silica tube fusing is encapsulated behind the pa, put into retort furnace, slowly rise to 900 ℃, its temperature rise rate is 10 ℃/hour, constant temperature 48 hours, take out after cooling, take out sample and grind mixing again, place silica tube to vacuumize encapsulation again, in retort furnace in 800 ℃ of sintering 48 hours, with its taking-up, put into mortar smash to pieces grind the preparation Powdered Li 2In 2SiS 6Compound.
Embodiment 3, prepare Powdered Li 2In 2SiS 6Compound:
Adopt Li 2S+In 2S 3+ Si+2S=Li 2In 2SiS 6Reaction formula prepares Li with solid reaction process 2In 2SiS 6Compound; Described Li 2S is 1.379 grams, described In 2S 3Be 9.775 grams, described Si is 0.843 gram, and described S is 1.924 gram, i.e. Li 2S: In 2S 3: Si: S=0.03mol: 0.03mol: 0.03mol: 0.06mol;
The concrete operations step is, the concrete operations step is, takes by weighing reagent respectively by above-mentioned dosage in glove box, and they are put into mortar, mixes and careful the grinding, in the silica tube of the Φ 12mm * 16mm that packs into then, is evacuated to 10 -3With flame the silica tube fusing is encapsulated behind the pa, put into retort furnace, slowly rise to 800 ℃, its temperature rise rate is 20 ℃/hour, constant temperature 72 hours, take out after cooling, take out sample and grind mixing again, place silica tube to vacuumize encapsulation again, in retort furnace in 800 ℃ of sintering 48 hours, with its taking-up, put into mortar smash to pieces grind Powdered Li 2In 2SiS 6Compound.
Embodiment 4, prepare Powdered Li 2In 2SiS 6Compound:
Adopt Li 2S+2In+3S+SiS 2=Li 2In 2SiS 6Reaction formula prepares Li with solid reaction process 2In 2SiS 6Compound; Described Li 2S is 1.379 grams, and described In is 6.889 grams, and described S is 2.886 grams, described SiS 2Be 2.767 gram, i.e. Li 2S: In: S: SiS 2=0.03mol: 0.06mol: 0.09mol: 0.03mol;
Its concrete operations step is, takes by weighing reagent respectively by above-mentioned dosage in glove box, and they are put into mortar, mixes and careful the grinding, in the silica tube of the Φ 12mm * 16mm that packs into then, is evacuated to 10 -3With flame the silica tube fusing is encapsulated behind the pa, put into retort furnace, slowly rise to 900 ℃, its temperature rise rate is 10 ℃/hour, constant temperature 48 hours, take out after cooling, take out sample and grind mixing again, place silica tube to vacuumize encapsulation again, in retort furnace in 800 ℃ of sintering 48 hours, with its taking-up, put into mortar smash to pieces grind the preparation Powdered Li 2In 2SiS 6Compound.
Embodiment 5, prepare Powdered Li 2In 2SiS 6Compound:
Adopt 2LiInS 2+ SiS 2=Li 2In 2SiS 6Reaction formula prepares Li with solid reaction process 2In 2SiS 6Compound; Described LiInS 2Be 11.153 grams, described SiS 2Be 2.767 gram, i.e. LiInS 2: SiS 2=0.06mol: 0.03mol;
Its concrete operations step is, takes by weighing reagent respectively by above-mentioned dosage in glove box, and they are put into mortar, mixes and careful the grinding, in the silica tube of the Φ 12mm * 16mm that packs into then, is evacuated to 10 -3With flame the silica tube fusing is encapsulated behind the pa, put into retort furnace, slowly rise to 800 ℃, its temperature rise rate is 30 ℃/hour, constant temperature 48 hours, take out after cooling, take out sample and grind mixing again, place silica tube to vacuumize encapsulation again, in retort furnace in 800 ℃ of sintering 48 hours, with its taking-up, put into mortar smash to pieces grind the preparation Powdered Li 2In 2SiS 6Compound products.
Embodiment 6, prepare Powdered Li 2In 2SiS 6Compound:
Adopt 2LiInS 2+ Si+2S=Li 2In 2SiS 6Reaction formula prepares Li with solid reaction process 2In 2SiS 6Compound; Described LiInS 2Be 11.153 grams, described Si is 0.843 gram, and described S is 1.924 gram, i.e. LiInS 2: Si: S=0.06mol: 0.03mol: 0.06mol;
Its concrete operations step is, takes by weighing reagent respectively by above-mentioned dosage in glove box, and they are put into mortar, mixes and careful the grinding, in the silica tube of the Φ 12mm * 16mm that packs into then, is evacuated to 10 -3With flame the silica tube fusing is encapsulated behind the pa, put into retort furnace, slowly rise to 900 ℃, its temperature rise rate is 10 ℃/hour, constant temperature 48 hours, take out after cooling, take out sample and grind mixing again, place silica tube to vacuumize encapsulation again, in retort furnace in 800 ℃ of sintering 48 hours, with its taking-up, put into mortar smash to pieces grind the preparation Powdered Li 2In 2SiS 6Compound.
Embodiment 7, adopt high-temperature fusant spontaneous crystallization legal system to be equipped with Li 2In 2SiS 6Crystal:
With the Li that obtains among the embodiment 1 to 6 2In 2SiS 6Powder is packed in the quartz glass tube of Φ 12mm * 16mm, is evacuated to 10 -3Behind the handkerchief, be placed in the tubular type growth furnace with oxyhydrogen flame encapsulation, slowly rise to 900 ℃, constant temperature 72 hours slowly is cooled to room temperature with the speed of 5 ℃/h, closes the tubular type growth furnace; Treat silica tube cooling back incision, can obtain faint yellow transparent Li 2In 2SiS 6Crystal.
Embodiment 8, adopt falling crucible method to prepare Li 2In 2SiS 6Crystal:
With the Li that obtains among the embodiment 1 to 6 2In 2SiS 6Powder is packed in the quartz glass tube of Φ 12mm * 16mm, is evacuated to 10 -3Behind the handkerchief, be placed in the crystal growing furnace with oxyhydrogen flame encapsulation, slowly rise to 900 ℃ raw material is melted fully after, growing apparatus vertically descends with 0.1-10mm/ hour speed; After crystal growth finished, growing apparatus was down to room temperature with 30 hours, obtained faint yellow transparent Li 2In 2SiS 6Crystal.
After tested, the prepared Li of above-described embodiment 7-8 2In 2SiS 6Non-linear optic crystal belongs to oblique system, and spacer is Cc, and its unit cell parameters is:
Figure BDA0000138595370000062
β=110.06 °, Z=4,
Figure BDA0000138595370000063
Has frequency-doubled effect; Fig. 2 is this Li 2In 2SiS 6The structural representation of non-linear optic crystal.
Embodiment 9:
Li with embodiment 7 and 8 gained 2In 2SiS 6Crystal is done to see through spectrometry, and this crystal is transparent in 0.35 μ m-18 mum wavelength scope; Not easily broken, be easy to cutting, polishing processing and preservation, not deliquescence; Li with embodiment 7,8 gained 2In 2SiS 6Crystal is placed on accompanying drawing 1 shown device label and is 3 position, and at room temperature, with transferring Q Ho:YAG laser apparatus to make light source, incident wavelength is the infrared light of 2090nm, and output wavelength is the frequency doubled light of 1045nm, and laser intensity is about AgGaS 2Half.
Accompanying drawing 1 is to adopt Li of the present invention 2In 2SiS 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, the 2nd, incoming laser beam, the 3rd, the Li after crystal aftertreatment and optics processing 2In 2SiS 6Non-linear optic crystal, the 4th, the outgoing laser beam that produces, the 5th, filter plate; Send incoming laser beam 2 by laser apparatus 1 and inject Li 2In 2SiS 6Single crystal 3, the outgoing laser beam 4 that produces passes through filter plate 5, and obtains needed laser beam;
Use Li of the present invention 2In 2SiS 6The device that non-linear optic crystal is made can be the frequency multiplication producer, upper and lower frequency converter, optical parametric oscillator etc.Laser apparatus 1 can be to mix ream yttrium aluminum garnet (Ho:YAG) laser apparatus or other laser apparatus, does the frequency doubling device of light source using the Ho:YAG laser apparatus, and incoming beam 2 is that wavelength is the infrared light of 2090nm, passes through Li 2In 2SiS 6It is 1045 frequency doubled light that non-linear optic crystal produces wavelength, and outgoing beam 4 contains fundamental frequency light that wavelength is 2090nm and the frequency doubled light of 1045nm, and the effect of filter plate 5 is elimination fundamental frequency light components, only allows frequency doubled light to pass through.

Claims (9)

1. a chemical formula is Li 2In 2SiS 6Compound.
2. described Li of claim 1 2In 2SiS 6The preparation method of compound, its step is as follows:
To contain the Li material, contain the In material, contain Si material and simple substance S according to mol ratio Li: In: Si: S=2: 2: 1: 6 ratio batching and mix after, be heated to 800-900 ℃ and carry out solid state reaction, obtaining chemical formula is Li 2In 2SiS 6Compound; The described Li of containing material is lithium sulfide or sulphur indium lithium; The described Si of containing material is elementary silicon or silicon disulfide; The described In of containing material is indium simple substance or indium trisulfide or sulphur indium lithium.
3. by the described Li of claim 2 2In 2SiS 6The preparation method of compound is characterized in that, the step that solid state reaction is carried out in described heating is: pack into after above-mentioned batching is ground in the silica tube, silica tube is evacuated to 10 -3Pa also melts encapsulation, puts into retort furnace, is warming up to 800-900 ℃ with 10-50 ℃/hour speed, constant temperature 48-72 hour, takes out sample after cooling; The sample that takes out is ground mixing again places silica tube to be evacuated to 10 again -3Pa also melts encapsulation, puts into retort furnace again and is warming up to 800-900 ℃ of sintering 48 hours; Sample is taken out, and smash to pieces grind Powdered Li 2In 2SiS 6Compound.
4. Li 2In 2SiS 6Non-linear optic crystal, this Li 2In 2SiS 6Non-linear optic crystal does not have symmetry centre, belongs to oblique system, and spacer is Cc, and its unit cell parameters is: a=12.074 (1)
Figure FDA0000138595360000011
, b=7.0221 (5)
Figure FDA0000138595360000012
, c=12.0802 (9)
Figure FDA0000138595360000013
, β=110.06 °.
5. described Li of claim 4 2In 2SiS 6The preparation method of non-linear optic crystal, it is high-temperature fusant spontaneous crystallization method growth Li 2In 2SiS 6Non-linear optic crystal the steps include: Powdered Li 2In 2SiS 6Compound be heated to melt high temperature solution and keep 24-96 hour after, be cooled to room temperature with 1-10 ℃/hour rate of temperature fall, obtain faint yellow transparent Li 2In 2SiS 6Crystal.
6. by the described Li of claim 5 2In 2SiS 6The preparation method of non-linear optic crystal is characterized in that, described Powdered Li 2In 2SiS 6Being prepared as follows of compound:
To contain the Li material, contain the In material, contain Si material and S according to mol ratio Li: In: Si: S=2: 2: 1: 6 mixed evenly after, solid state reaction is carried out in heating, obtaining chemical formula is Li 2In 2SiS 6Compound, through smash to pieces grind Powdered Li 2In 2SiS 6Compound; The described Li of containing material is lithium sulfide or sulphur indium lithium; The described Si of containing material is elementary silicon or silicon disulfide; The described In of containing material is indium simple substance or indium trisulfide or sulphur indium lithium.
7. described Li of claim 4 2In 2SiS 6The preparation method of non-linear optic crystal, it is Bridgman-Stockbarge method for growing Li 2In 2SiS 6Non-linear optic crystal, its step is as follows:
With Li 2In 2SiS 6Powder is put into crystal growing apparatus, slowly is warming up to powder smelting, treat that powder melts fully after, crystal growing apparatus vertically descends with the speed of 0.1-10mm/h, carries out Li in crystal growing apparatus decline process 2In 2SiS 6The non-linear optic crystal growth, its growth cycle is 5-20 days.
8. by the described Li of claim 7 2In 2SiS 6The preparation method of non-linear optic crystal is characterized in that, also comprises Li 2In 2SiS 6The aftertreatment of non-linear optic crystal: after crystal growth finishes, will crystal stay in the growth furnace and anneal, be cooled to room temperature with 20～50 ℃/hour speed.
9. described Li of claim 4 2In 2SiS 6The purposes of non-linear optic crystal is characterized in that, this Li 2In 2SiS 6Non-linear optic crystal is for the preparation of device for non-linear optical, and prepared device for non-linear optical comprises a branch of at least incidence electromagnetic radiation by at least one Li 2In 2SiS 6Produce the device that a branch of at least frequency is different from the output radiation of incidence electromagnetic radiation behind the non-linear optic crystal.
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Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101767778A (en) * 2010-02-03 2010-07-07 中国科学院理化技术研究所 BaCa4Se7 compound, BaCa4Se7 nonlinear optical crystal, preparation method and application
CN102094245A (en) * 2010-12-08 2011-06-15 中国科学院理化技术研究所 Selenium-gallium-aluminum-barium compound, selenium-gallium-aluminum-barium nonlinear optical crystal and preparation methods and applications of compound and nonlinear optical crystal

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101767778A (en) * 2010-02-03 2010-07-07 中国科学院理化技术研究所 BaCa4Se7 compound, BaCa4Se7 nonlinear optical crystal, preparation method and application
CN102094245A (en) * 2010-12-08 2011-06-15 中国科学院理化技术研究所 Selenium-gallium-aluminum-barium compound, selenium-gallium-aluminum-barium nonlinear optical crystal and preparation methods and applications of compound and nonlinear optical crystal

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
YOUNGSIK KIM: "Characterization of New Infrared Nonlinear Optical Material with High Laser Damage Threshold, Li2Ga2GeS6", 《CHEMISTRY OF MATERIALS》, vol. 20, no. 19, 21 August 2008 (2008-08-21), pages 6048 - 6052 *
介万奇: "《晶体生长原理与技术》", 30 September 2010, 科学出版社, article "固相反应合成", pages: 257-258 *

Cited By (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103866391A (en) * 2014-03-21 2014-06-18 中国科学院福建物质结构研究所 Infrared nonlinear optical powder and mono-crystal 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
CN105350082A (en) * 2015-11-18 2016-02-24 中国科学院理化技术研究所 Na2In2GeSe6 nonlinear optical crystal and preparation method and use thereof
CN105350082B (en) * 2015-11-18 2018-07-03 中国科学院理化技术研究所 A kind of Na2In2GeSe6Nonlinear optical crystal and preparation method and purposes
US10923763B2 (en) 2019-01-31 2021-02-16 University Of Maryland, College Park Lithium metal sulfides as lithium super ionic conductors, solid electrolyte and coating layer for lithium metal battery and lithium-ion battery
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CN112064118A (en) * 2020-08-12 2020-12-11 三明学院 Diamond-like infrared nonlinear optical crystal and preparation method thereof
CN112064118B (en) * 2020-08-12 2021-09-24 三明学院 Diamond-like infrared nonlinear optical crystal and preparation method thereof

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