CN103060917B - BaGa2SiS6Compound and BaGa2SiS6Nonlinear optical crystal and its preparation method and use - Google Patents
BaGa2SiS6Compound and BaGa2SiS6Nonlinear optical crystal and its preparation method and use Download PDFInfo
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- CN103060917B CN103060917B CN201110319535.1A CN201110319535A CN103060917B CN 103060917 B CN103060917 B CN 103060917B CN 201110319535 A CN201110319535 A CN 201110319535A CN 103060917 B CN103060917 B CN 103060917B
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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 19
- 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
- 239000000463 material Substances 0.000 claims description 25
- 239000000126 substance Substances 0.000 claims description 14
- 239000000843 powder Substances 0.000 claims description 5
- 230000005670 electromagnetic radiation Effects 0.000 claims description 4
- 238000010671 solid-state reaction Methods 0.000 claims description 4
- WHBHBVVOGNECLV-OBQKJFGGSA-N 11-deoxycortisol Chemical compound O=C1CC[C@]2(C)[C@H]3CC[C@](C)([C@@](CC4)(O)C(=O)CO)[C@@H]4[C@@H]3CCC2=C1 WHBHBVVOGNECLV-OBQKJFGGSA-N 0.000 claims description 3
- GYHNNYVSQQEPJS-UHFFFAOYSA-N Gallium Chemical compound [Ga] GYHNNYVSQQEPJS-UHFFFAOYSA-N 0.000 claims description 3
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 3
- 229910052788 barium Inorganic materials 0.000 claims description 3
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 claims description 3
- CJDPJFRMHVXWPT-UHFFFAOYSA-N barium sulfide Chemical compound [S-2].[Ba+2] CJDPJFRMHVXWPT-UHFFFAOYSA-N 0.000 claims description 3
- 229910052733 gallium Inorganic materials 0.000 claims description 3
- 239000000203 mixture Substances 0.000 claims description 3
- 229910052710 silicon Inorganic materials 0.000 claims description 3
- 239000010703 silicon Substances 0.000 claims description 3
- KHDSWONFYIAAPE-UHFFFAOYSA-N silicon sulfide Chemical compound S=[Si]=S KHDSWONFYIAAPE-UHFFFAOYSA-N 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
- 239000000377 silicon dioxide Substances 0.000 description 22
- 229910020346 SiS 2 Inorganic materials 0.000 description 20
- 238000006243 chemical reaction Methods 0.000 description 18
- 239000004570 mortar (masonry) Substances 0.000 description 16
- 238000005538 encapsulation Methods 0.000 description 12
- 238000001816 cooling Methods 0.000 description 10
- 238000002156 mixing Methods 0.000 description 10
- 239000007787 solid Substances 0.000 description 10
- 239000003153 chemical reaction reagent Substances 0.000 description 8
- 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
- 238000005245 sintering 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
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- 208000014674 injury Diseases 0.000 description 1
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- 238000003199 nucleic acid amplification method Methods 0.000 description 1
- 230000005693 optoelectronics Effects 0.000 description 1
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- 239000002994 raw material Substances 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 present invention relates to BaGa2SiS6Compound and BaGa2SiS6Nonlinear optical crystal and its preparation method and application; the BaGa2SiS6The compound is prepared by adopting a solid-phase reaction; BaGa2SiS6The nonlinear optical crystal grows by adopting a high-temperature melt spontaneous crystallization method or a Bridgman method; in the BaGa2SiS6The 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 BaGa2SiS6The 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 BaGa2SiS6The nonlinear optical crystal can be used for manufacturing nonlinear optical devices.
Description
Technical field
The present invention relates to a kind of BaGa
2siS
6compound, BaGa
2siS
6non-linear optic crystal (BaGa
2siS
6monocrystalline) and this BaGa
2siS
6the preparation method of monocrystalline and this BaGa
2siS
6the purposes of device for non-linear optical of monocrystalline for making.
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 BaGa
2siS
6compound.
Another object of the present invention is to provide a kind of BaGa
2siS
6non-linear optic crystal.
Still a further object of the present invention is to provide BaGa
2siS
6the preparation method of non-linear optic crystal.
A further object of the invention is to provide BaGa
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 BaGa
2siS
6compound.
BaGa provided by the invention
2siS
6the preparation method of compound, its step is as follows:
By containing Ba material, containing Ga material, to prepare burden according to the ratio of mol ratio Ba:Ga:Si:S=1:2:1:6 containing Si material and simple substance S and after mixing, be heated to 800-1000 DEG C carry out solid state reaction and (in principle, adopt general chemical synthesis process to prepare BaGa
2siS
6compound; The preferred solid reaction process of the present invention), obtaining chemical formula is BaGa
2siS
6compound; Described is barium simple substance or barium sulphide containing Ba material; Described is elementary silicon or silicon disulfide containing Si material; Described is gallium simple substance or trisulfides two galliums containing Ga 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 10-60 DEG C/h to 800-1000 DEG C, constant temperature 48 hours, 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 700-950 DEG C of sintering 24 hours; Sample is taken out, and smashs to pieces and grind to obtain Powdered BaGa
2siS
6compound.
Described BaGa
2siS
6compound can be prepared by following chemical equation:
(1)BaS+Ga
2S
3+SiS
2=BaGa
2SiS
6;
(2)BaS+2Ga+Si+5S=BaGa
2SiS
6;
(3)BaS+Ga
2S
3+Si+2S=BaGa
2SiS
6;
(4)BaS+2Ga+3S+SiS
2=BaGa
2SiS
6;
(5)Ba+2Ga+Si+6S=BaGa
2SiS
6;
(6)Ba+S+Ga
2S
3+SiS
2=BaGa
2SiS
6;
(7)Ba+4S+2Ga+SiS
2=BaGa
2SiS
6;
(8)Ba+3S+Ga
2S
3+Si=BaGa
2SiS
6;
BaGa provided by the invention
2siS
6non-linear optic crystal does not have symmetry centre, and belong to trigonal system, spacer is R3, and its unit cell parameters is:
α=β=90 °, γ=120 °, Z=3,
BaGa provided by the invention
2siS
6the preparation method of non-linear optic crystal, it is high-temperature fusant spontaneous crystallization method growth BaGa
2siS
6non-linear optic crystal, the steps include: Powdered BaGa
2siS
6compound is heated to melt to obtain high temperature solution after keeping 48-96 hour, be cooled to room temperature with the rate of temperature fall of 2-5 DEG C/h, obtains the BaGa of pale yellow transparent
2siS
6crystal.
Described Powdered BaGa
2siS
6being prepared as follows of compound:
By containing Ba material, containing Ga material, to prepare burden according to the ratio of mol ratio Ba:Ga:Si:S=1:2:1:6 containing Si material and simple substance S and after mixing, be heated to 800-1000 DEG C carry out solid state reaction and (in principle, adopt general chemical synthesis process to prepare BaGa
2siS
6compound; The preferred solid reaction process of the present invention), obtaining chemical formula is BaGa
2siS
6compound; Described is barium simple substance or barium sulphide containing Ba material; Described is elementary silicon or silicon disulfide containing Si material; Described is gallium simple substance or trisulfides two galliums containing Ga material.
Described BaGa
2siS
6compound can be prepared by following chemical equation:
(1)BaS+Ga
2S
3+SiS
2=BaGa
2SiS
6;
(2)BaS+2Ga+Si+5S=BaGa
2SiS
6;
(3)BaS+Ga
2S
3+Si+2S=BaGa
2SiS
6;
(4)BaS+2Ga+3S+SiS
2=BaGa
2SiS
6;
(5)Ba+2Ga+Si+6S=BaGa
2SiS
6;
(6)Ba+S+Ga
2S
3+SiS
2=BaGa
2SiS
6;
(7)Ba+4S+2Ga+SiS
2=BaGa
2SiS
6;
(8)Ba+3S+Ga
2S
3+Si=BaGa
2SiS
6;
BaGa provided by the invention
2siS
6a preparation method again of non-linear optic crystal, it is Bridgman-Stockbarge method for growing BaGa
2siS
6non-linear optic crystal, its step is as follows:
By Powdered BaGa
2siS
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 0.1-1.0mm/h, in crystal growing apparatus decline process, carry out BaGa
2siS
6non-linear optic crystal grows, and its growth cycle is 10-20 days;
Bridgman-Stockbarge method for growing BaGa of the present invention
2siS
6non-linear optic crystal also comprises BaGa
2siS
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 30 ~ 50 DEG C/h) with the speed of 30 ~ 100 DEG C/h.
Adopt above-mentioned two kinds of methods all can obtain the BaGa being of a size of centimetre-sized
2siS
6non-linear optic crystal; Use large size crucible, and extend vegetative period, then can obtain corresponding large-size BaGa
2siS
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 BaGa
2siS
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 BaGa further
2siS
6the purposes of non-linear optic crystal, this BaGa
2siS
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 this BaGa
2siS
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.
BaGa of the present invention
2siS
6compound, this compound non-linear optic crystal and its production and use there is following effect:
At this BaGa
2siS
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 BaGa obtained
2siS
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 BaGa
2siS
6non-linear optic crystal can be used for making device for non-linear optical.
Accompanying drawing explanation
Fig. 1 adopts BaGa of the present invention
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, and 2 is incoming laser beams, and 3 is the BaGa after crystal aftertreatment and optical manufacturing
2siS
6non-linear optic crystal, 4 is produced outgoing laser beams, and 5 is filter plates.
Fig. 2 is BaGa
2siS
6the structural representation of non-linear optic crystal.
Embodiment
Embodiment 1, prepares Powdered BaGa
2siS
6compound:
Adopt BaS+Ga
2s
3+ SiS
2=BaGa
2siS
6reaction formula solid reaction process prepares BaGa
2siS
6compound;
Described BaS is 3.388 grams, described Ga
2s
3be 4.713 grams, described SiS
2it is 1.844 grams; I.e. BaS:Ga
2s
3: SiS
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 hours, takes out after cooling, taking-up sample is reground, be placed in silica tube again and vacuumize encapsulation, in retort furnace, sinter 24 hours in 700 DEG C, now, taken out, put into mortar and smash to pieces and grind to obtain Powdered BaGa
2siS
6compound products.
Embodiment 2, prepares Powdered BaGa
2siS
6compound:
Adopt BaS+2Ga+Si+5S=BaGa
2siS
6reaction formula solid reaction process prepares BaGa
2siS
6compound; Described BaS is 3.388 grams, and described Ga is 2.789 grams, and described Si is 0.562 gram, and described S is 3.207 grams, i.e. BaS:Ga:Si:S=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
-3after pa with flame by silica tube fusing encapsulation, put into retort furnace, slowly rise to 1000 DEG C, its temperature rise rate is 10 DEG C/h, and constant temperature 48 hours, takes out after cooling, put into mortar smash to pieces grind to obtain preparation Powdered BaGa
2siS
6compound products.
Embodiment 3, prepares Powdered BaGa
2siS
6compound:
Adopt BaS+Ga
2s
3+ Si+2S=BaGa
2siS
6; Reaction formula solid reaction process prepares BaGa
2siS
6compound; Described BaS is 3.388 grams, described Ga
2s
3be 4.713 grams, described Si is 0.562 gram, and described S is 1.283 grams, i.e. BaS:Ga
2s
3: Si:S=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
-3after pa with flame by silica tube fusing encapsulation, put into retort furnace, rise to 750 DEG C, its temperature rise rate is 60 DEG C/h, and constant temperature 48 hours, takes out after cooling, puts into mortar and smashs to pieces and grind to obtain Powdered BaGa
2siS
6compound products.
Embodiment 4, prepares Powdered BaGa
2siS
6compound:
Adopt BaS+2Ga+3S+SiS
2=BaGa
2siS
6reaction formula solid reaction process prepares BaGa
2siS
6compound; Described BaS is 3.388 grams, and described Ga is 2.789 grams, and described S is 1.924 grams, described SiS
2be 1.844 grams, i.e. BaS:Ga:S:SiS
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 1000 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 900 DEG C of sintering 24 hours in retort furnace, taken out, put into mortar smash to pieces grind to obtain preparation Powdered BaGa
2siS
6compound products.
Embodiment 5, prepares Powdered BaGa
2siS
6compound:
Adopt Ba+2Ga+Si+6S=BaGa
2siS
6reaction formula solid reaction process prepares BaGa
2siS
6compound; Described Ba is 2.747 grams, and described Ga is 2.789 grams, and described Si is 0.562 gram, and described S is 3.848 grams, i.e. Ba:Ga:Si:S=0.02mol:0.04mol:0.02mol:0.12mol;
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
-3after pa with flame by silica tube fusing encapsulation, put into retort furnace, slowly rise to 1000 DEG C, its temperature rise rate is 30 DEG C/h, and constant temperature 48 hours, takes out after cooling, put into mortar smash to pieces grind to obtain preparation Powdered BaGa
2siS
6compound products.
Embodiment 6, prepares Powdered BaGa
2siS
6compound:
Adopt Ba+S+Ga
2s
3+ SiS
2=BaGa
2siS
6reaction formula solid reaction process prepares BaGa
2siS
6compound; Described Ba is 2.747 grams, described Ga
2s
3be 4.713 grams, described SiS
2be 1.844 grams, described S is 0.641 gram, i.e. Ba:Ga
2s
3: SiS
2: S=0.02mol:0.02mol:0.02mol: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
-3after pa with flame by silica tube fusing encapsulation, put into retort furnace, slowly rise to 1000 DEG C, its temperature rise rate is 30 DEG C/h, and constant temperature 48 hours, takes out after cooling, put into mortar smash to pieces grind to obtain preparation Powdered BaGa
2siS
6compound products.
Embodiment 7, prepares Powdered BaGa
2siS
6compound:
Adopt Ba+4S+2Ga+SiS
2=BaGa
2siS
6reaction formula solid reaction process prepares BaGa
2siS
6compound; Described Ba is 2.747 grams, and described Ga is 2.789 grams, described SiS
2be 1.844 grams, described S is 2.565 grams, i.e. Ba:Ga:SiS
2: S=0.02mol:0.04mol:0.02mol:0.08mol;
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
-3after pa with flame by silica tube fusing encapsulation, put into retort furnace, slowly rise to 1000 DEG C, its temperature rise rate is 30 DEG C/h, and constant temperature 48 hours, takes out after cooling, put into mortar smash to pieces grind to obtain preparation Powdered BaGa
2siS
6compound products.
Embodiment 8, prepares Powdered BaGa
2siS
6compound:
Adopt Ba+3S+Ga
2s
3+ Si=BaGa
2siS
6reaction formula solid reaction process prepares BaGa
2siS
6compound; Described Ba is 2.747 grams, described Ga
2s
3be 4.713 grams, described Si is 0.562 gram, and described S is 1.924 grams, i.e. Ba:Ga
2s
3: Si:S=0.02mol:0.02mol:0.02mol:0.06mol;
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
-3after pa with flame by silica tube fusing encapsulation, put into retort furnace, slowly rise to 1000 DEG C, its temperature rise rate is 10 DEG C/h, and constant temperature 48 hours, takes out after cooling, put into mortar smash to pieces grind to obtain preparation Powdered BaGa
2siS
6compound products.
Embodiment 9, adopts high-temperature fusant spontaneous crystallization legal system for BaGa
2siS
6crystal:
By the BaGa obtained in embodiment 1 to 8
2siS
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 1000 DEG C, constant temperature 72 hours, with the speed slow cooling of 2-5 DEG C/h to room temperature, close tubular type growth furnace; Cut after silica tube cooling, the BaGa of pale yellow transparent can be obtained
2siS
6crystal.
Embodiment 10, adopts falling crucible method to prepare BaGa
2siS
6crystal:
By the BaGa obtained in embodiment 1 to 8
2siS
6powder loads in the quartz glass tube of Φ 15mm × 18mm, is evacuated to 10
-3after handkerchief, with oxyhydrogen flame encapsulation be placed in crystal growing furnace, slowly rise to 1000 DEG C raw material is melted completely after, growing apparatus vertically declines with the speed of 0.1-1.0mm/ hour; After crystal growth terminates, growing apparatus was down to room temperature with 30 hours, obtained the BaGa of pale yellow transparent
2siS
6crystal.
After tested, the BaGa prepared by above-described embodiment 9-10
2siS
6non-linear optic crystal belongs to trigonal system, and spacer is R3, and its unit cell parameters is:
α=β=90 °, γ=120 °, Z=3,
there is frequency-doubled effect; Fig. 2 is this BaGa
2siS
6the structural representation of non-linear optic crystal.
Embodiment 11:
By the BaGa of embodiment 9 and 10 gained
2siS
6crystal is done through spectrometry, and this crystal is transparent within the scope of 0.35 μm of-13 mum wavelength; Not easily broken, be easy to cutting, polishing and preservation, not deliquescence; By the BaGa of embodiment 9 and 10 gained
2siS
6crystal, being placed on accompanying drawing 1 shown device label is the position of 3, and at room temperature, with the Ho:Tm:Cr:YAG laser light source adjusting Q, incident wavelength is the infrared light of 2090nm, and output wavelength is the frequency doubled light of 1045nm, laser intensity and AgGaS
2quite.
Accompanying drawing 1 adopts BaGa of the present invention
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, and 2 is incoming laser beams, and 3 is the BaGa after crystal aftertreatment and optical manufacturing
2siS
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 BaGa
2siS
6single crystal 3, the outgoing laser beam 4 produced is by filter plate 5, and the laser beam required for obtaining;
Use BaGa of the present invention
2siS
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 the Ho:Tm:Cr:YAG laser light source adjusting Q, the infrared light of incoming beam 2 to be wavelength be 2090nm, passes through BaGa
2siS
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 BaGa
2siS
6non-linear optic crystal, this BaGa
2siS
6non-linear optic crystal does not have symmetry centre, and belong to trigonal system, spacer is R3, and its unit cell parameters is:
α=β=90 °, γ=120 °, Z=3,
2. BaGa described in a claim 1
2siS
6the preparation method of non-linear optic crystal, it is high-temperature fusant spontaneous crystallization method growth BaGa
2siS
6non-linear optic crystal, the steps include: Powdered BaGa
2siS
6compound is heated to melt to obtain high temperature solution after keeping 48-96 hour, be cooled to room temperature with the rate of temperature fall of 2-5 DEG C/h, obtains the BaGa of pale yellow transparent
2siS
6crystal.
3. by BaGa described in claim 2
2siS
6the preparation method of non-linear optic crystal, is characterized in that, described Powdered BaGa
2siS
6being prepared as follows of compound:
By containing Ba material, containing Ga material, mix according to the ratio of mol ratio Ba:Ga:Si:S=1:2:1:6 containing Si material and simple substance S after, heating carry out solid state reaction, obtaining chemical formula is BaGa
2siS
6compound, grind to obtain Powdered BaGa through smashing to pieces
2siS
6compound; Described is barium simple substance or barium sulphide containing Ba material; Described is elementary silicon or silicon disulfide containing Si material; Described is gallium simple substance or trisulfides two galliums containing Ga material.
4. BaGa described in a claim 1
2siS
6the preparation method of non-linear optic crystal, it is Bridgman-Stockbarge method for growing BaGa
2siS
6non-linear optic crystal, its step is as follows:
By BaGa
2siS
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 0.1-1.0mm/h, in crystal growing apparatus decline process, carry out BaGa
2siS
6non-linear optic crystal grows, and its growth cycle is 10-20 days.
5. by BaGa described in claim 4
2siS
6the preparation method of non-linear optic crystal, is characterized in that, also comprises BaGa
2siS
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 30 ~ 100 DEG C/h.
6. a BaGa according to claim 1
2siS
6the purposes of non-linear optic crystal, is characterized in that, this BaGa
2siS
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 this BaGa
2siS
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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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 |
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CN101545141A (en) * | 2008-03-25 | 2009-09-30 | 中国科学院福建物质结构研究所 | Sulfurized gallium and barium monocrystal as well as growing method and infrared nonlinear optical device thereof |
CN101767778A (en) * | 2010-02-03 | 2010-07-07 | 中国科学院理化技术研究所 | BaGa4Se7Compound and BaGa4Se7Nonlinear optical crystal and its preparation method and use |
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CN1200581A (en) * | 1997-05-22 | 1998-12-02 | 松下电器产业株式会社 | Non-aqueous electrolyte secondary battery |
CN101545141A (en) * | 2008-03-25 | 2009-09-30 | 中国科学院福建物质结构研究所 | Sulfurized gallium and barium monocrystal as well as growing method and infrared nonlinear optical device thereof |
CN101767778A (en) * | 2010-02-03 | 2010-07-07 | 中国科学院理化技术研究所 | BaGa4Se7Compound and BaGa4Se7Nonlinear optical crystal and its preparation method and use |
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