CN102976287A - BaGa2GeSe6Compound and BaGa2GeSe6Nonlinear optical crystal and its preparation method and use - Google Patents
BaGa2GeSe6Compound and BaGa2GeSe6Nonlinear optical crystal and its preparation method and use Download PDFInfo
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- CN102976287A CN102976287A CN2011102582978A CN201110258297A CN102976287A CN 102976287 A CN102976287 A CN 102976287A CN 2011102582978 A CN2011102582978 A CN 2011102582978A CN 201110258297 A CN201110258297 A CN 201110258297A CN 102976287 A CN102976287 A CN 102976287A
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- 239000013078 crystal Substances 0.000 title claims abstract description 98
- 230000003287 optical effect Effects 0.000 title claims abstract description 32
- 238000002360 preparation method Methods 0.000 title claims abstract description 21
- 238000000034 method Methods 0.000 claims abstract description 9
- 150000001875 compounds Chemical class 0.000 claims abstract description 8
- 238000003746 solid phase reaction Methods 0.000 claims abstract description 7
- 238000002425 crystallisation Methods 0.000 claims abstract description 4
- 230000002269 spontaneous effect Effects 0.000 claims abstract description 4
- 229910005866 GeSe Inorganic materials 0.000 claims description 151
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 56
- 239000000463 material Substances 0.000 claims description 33
- 239000000377 silicon dioxide Substances 0.000 claims description 27
- 239000000126 substance Substances 0.000 claims description 27
- 238000005538 encapsulation Methods 0.000 claims description 14
- 238000001816 cooling Methods 0.000 claims description 11
- 238000005245 sintering Methods 0.000 claims description 6
- 238000010671 solid-state reaction Methods 0.000 claims description 6
- 238000010792 warming Methods 0.000 claims description 6
- 239000000843 powder Substances 0.000 claims description 5
- 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 4
- GYHNNYVSQQEPJS-UHFFFAOYSA-N Gallium Chemical compound [Ga] GYHNNYVSQQEPJS-UHFFFAOYSA-N 0.000 claims description 4
- 229910052788 barium Inorganic materials 0.000 claims description 4
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 claims description 4
- RJWLRCHYHHXJLX-UHFFFAOYSA-N barium(2+);selenium(2-) Chemical compound [Se-2].[Ba+2] RJWLRCHYHHXJLX-UHFFFAOYSA-N 0.000 claims description 4
- 230000005670 electromagnetic radiation Effects 0.000 claims description 4
- 229910052733 gallium Inorganic materials 0.000 claims description 4
- 229910052732 germanium Inorganic materials 0.000 claims description 4
- GNPVGFCGXDBREM-UHFFFAOYSA-N germanium atom Chemical compound [Ge] GNPVGFCGXDBREM-UHFFFAOYSA-N 0.000 claims description 4
- 239000000155 melt Substances 0.000 claims description 4
- 238000010438 heat treatment Methods 0.000 claims description 3
- 239000000203 mixture Substances 0.000 claims description 3
- 125000006850 spacer group Chemical group 0.000 claims description 3
- 230000007423 decrease Effects 0.000 claims description 2
- 230000005855 radiation Effects 0.000 claims description 2
- 238000003723 Smelting Methods 0.000 claims 1
- 238000012545 processing Methods 0.000 abstract description 5
- 238000004519 manufacturing process Methods 0.000 abstract description 2
- 238000005336 cracking Methods 0.000 abstract 1
- 238000003860 storage Methods 0.000 abstract 1
- 238000006243 chemical reaction Methods 0.000 description 18
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- 239000007787 solid Substances 0.000 description 10
- 239000003153 chemical reaction reagent Substances 0.000 description 8
- 238000005303 weighing Methods 0.000 description 8
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- 229910019655 synthetic inorganic crystalline material Inorganic materials 0.000 description 3
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- 238000003199 nucleic acid amplification method 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
- 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
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- 238000005520 cutting process Methods 0.000 description 1
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- 238000004611 spectroscopical analysis Methods 0.000 description 1
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- 229910019901 yttrium aluminum garnet Inorganic materials 0.000 description 1
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Abstract
The invention relates to a BaGa2GeSe6Compound and BaGa2GeSe6Nonlinear optical crystal and its preparation method and application; the BaGa2GeSe6The compound is prepared by adopting a solid-phase reaction; BaGa2GeSe6The nonlinear optical crystal grows by adopting a high-temperature melt spontaneous crystallization method or a Bridgman method; in the BaGa2GeSe6The crystal is easy to grow in the growth of the nonlinear optical crystal, is transparent and has no package, and has the advantages of higher growth speed, lower growth temperature, low cost, easy obtainment of crystals with larger size and the like; obtained BaGa2GeSe6The 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 BaGa2GeSe6The nonlinear optical crystal can be used for manufacturing nonlinear optical devices.
Description
Technical field
The present invention relates to a kind of BaGa
2GeSe
6Compound, BaGa
2GeSe
6Non-linear optic crystal (BaGa
2GeSe
6Monocrystalline) and this BaGa
2GeSe
6The preparation method of monocrystalline and this BaGa
2GeSe
6Monocrystalline is used for the purposes of the device for non-linear optical of making.
Background technology
Crystal with non-linear optical effect is called non-linear optic crystal.Here non-linear optical effect refers to the effects such as frequency multiplication and frequency, difference frequency, parameter amplification.Only have 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, the 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 the requirement of practical application; Such 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 such as AgGaQ
2(Q=S, Se, Te), the too low and crystal growth difficulty of the light injury threshold of infrared non-linear crystal has directly affected actual use.The middle-infrared band non-linear optic crystal has important application at optoelectronic areas, can the laser (such as 1.064 μ m) of near-infrared band be extended to middle infrared by means such as optical parametric oscillation or optical parameter amplifications such as it; Also can be to the important laser in mid-infrared light district (such 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 BaGa that the object of the invention is to provide a kind of chemical formula
2GeSe
6Compound.
Another purpose of the present invention is to provide a kind of novel infrared nonlinear optical crystal material BaGa of premium properties
2GeSe
6Non-linear optic crystal.
Still a further object of the present invention is to provide the novel infrared nonlinear optical crystal material B aGa of this premium properties
2GeSe
6The preparation method of non-linear optic crystal.
A further object of the invention is to provide BaGa
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 BaGa
2GeSe
6Compound.
BaGa provided by the invention
2GeSe
6The preparation method of compound, its step is as follows:
To contain the Ba material, contain the Ga material, contain Ge material and simple substance Se according to mol ratio Ba: Ga: Ge: Se=1: 2: 1: 6 ratio batching and mix after, be heated to 850-950 ℃ and carry out solid state reaction to obtain chemical formula be BaGa
2GeSe
6Compound (in principle, adopt general chemical synthesis process can prepare BaGa
2GeSe
6Compound; The preferred solid reaction process of the present invention); The described Ba of containing material is barium simple substance or barium selenide; The described Ge of containing material is germanium simple substance or two Germanium selenide; The described Ga of containing material is gallium simple substance or three selenizings, two galliums.
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 850-950 ℃ with 10-50 ℃/hour speed, and constant temperature 48 hours takes out sample after cooling; The sample that takes out is reground places again silica tube to be evacuated to 10
-3Pa also melts encapsulation, puts into retort furnace again and is warming up to 850-950 ℃ of sintering 24 hours; Sample is taken out and smashs to pieces and grind to get Powdered BaGa
2GeSe
6Compound.
Described BaGa
2GeSe
6Compound can prepare by following chemical equation:
(1)BaSe+Ga
2Se
3+GeSe
2＝BaGa
2GeSe
6；
(2)BaSe+2Ga+Ge+5Se＝BaGa
2GeSe
6；
(3)BaSe+Ga
2Se
3+Ge+2Se＝BaGa
2GeSe
6；
(4)BaSe+2Ga+3Se+GeSe
2＝BaGa
2GeSe
6；
(5)Ba+2Ga+Ge+6Se＝BaGa
2GeSe
6；
(6)Ba+Se+Ga
2Se
3+GeSe
2＝BaGa
2GeSe
6；
(7)Ba+4Se+2Ga+GeSe
2＝BaGa
2GeSe
6；
(8)Ba+3Se+Ga
2Se
3+Ge＝BaGa
2GeSe
6；
BaGa provided by the invention
2GeSe
6Non-linear optic crystal does not possess symmetry centre, belongs to trigonal system, and spacer is R3, and its unit cell parameters is: a=b=10.008 (1)
C=9.090 (2)
α=β=90 °, γ=120 °, Z=3, V=788.4
BaGa provided by the invention
2GeSe
6The preparation method of non-linear optic crystal, it is high-temperature fusant spontaneous crystallization method growth BaGa
2GeSe
6Non-linear optic crystal the steps include: Powdered BaGa
2GeSe
6Compound be heated to melt high temperature solution and keep 48-96 hour after, be cooled to room temperature with 3-5 ℃/hour rate of temperature fall, obtain red transparent BaGa
2GeSe
6Crystal.
Described Powdered BaGa
2GeSe
6Being prepared as follows of compound:
To contain the Ba material, contain the Ga material, contain Ge material and simple substance Se according to mol ratio Ba: Ga: Ge: Se=1: 2: 1: 6 ratio batching and mix after, be heated to 850-950 ℃ and carry out solid state reaction to obtain chemical formula be BaGa
2GeSe
6Compound (in principle, adopt general chemical synthesis process can prepare BaGa
2GeSe
6Compound; The preferred solid reaction process of the present invention); The described Ba of containing material is barium simple substance or barium selenide; The described Ge of containing material is germanium simple substance or two Germanium selenide; The described Ga of containing material is gallium simple substance or three selenizings, two galliums.
BaGa of the present invention
2GeSe
6Compound can prepare by following chemical equation:
(1)BaSe+Ga
2Se
3+GeSe
2＝BaGa
2GeSe
6；
(2)BaSe+2Ga+Ge+5Se＝BaGa
2GeSe
6；
(3)BaSe+Ga
2Se
3+Ge+2Se＝BaGa
2GeSe
6；
(4)BaSe+2Ga+3Se+GeSe
2＝BaGa
2GeSe
6；
(5)Ba+2Ga+Ge+6Se＝BaGa
2GeSe
6；
(6)Ba+Se+Ga
2Se
3+GeSe
2＝BaGa
2GeSe
6；
(7)Ba+4Se+2Ga+GeSe
2＝BaGa
2GeSe
6；
(8)Ba+3Se+Ga
2Se
3+Ge＝BaGa
2GeSe
6。
BaGa provided by the invention
2GeSe
6An again preparation method of non-linear optic crystal, it is Bridgman-Stockbarge method for growing BaGa
2GeSe
6Non-linear optic crystal, its step is as follows:
With Powdered BaGa
2GeSe
6Compound is put into crystal growing apparatus, slowly is warming up to its fusing, and after it melted fully, crystal growing apparatus vertically descended with the speed of 0.1-1.0mm/h, carries out BaGa in crystal growing apparatus decline process
2GeSe
6The non-linear optic crystal growth, its growth cycle is 10-20 days;
Bridgman-Stockbarge method for growing BaGa of the present invention
2GeSe
6Non-linear optic crystal also comprises BaGa
2GeSe
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 (30～50 ℃/hour of preferred rate of temperature fall) with the speed that is not more than 30～100 ℃/hour.
Adopt above-mentioned two kinds of methods all can obtain to be of a size of the BaGa of centimetre-sized
2GeSe
6Non-linear optic crystal; Use the large size crucible, and prolong vegetative period, then can obtain corresponding large-size BaGa
2GeSe
6Non-linear optic crystal.
According to the crystallography data of crystal, the crystal blank is directed, 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 BaGa
2GeSe
6Non-linear optic crystal has physical and chemical performance to be stablized, and hardness is larger, and good mechanical property is not easily broken, is difficult for deliquescence, is easy to the advantages such as processing and preservation; So the present invention also further provides BaGa
2GeSe
6The purposes of non-linear optic crystal, this BaGa
2GeSe
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 this BaGa
2GeSe
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.
BaGa of the present invention
2GeSe
6Compound, the non-linear optic crystal of this compound and its production and use have following effect:
At this BaGa
2GeSe
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 growth temperature is low, and cost is low, obtains easily the advantages such as large-size crystal; The BaGa that obtains
2GeSe
6Non-linear optic crystal has wider transmission region, and hardness is larger, good mechanical property, and not easily broken and deliquescence is easy to the advantages such as processing and preservation; This BaGa
2GeSe
6Non-linear optic crystal can be used for making device for non-linear optical.
Description of drawings
Fig. 1 adopts BaGa of the present invention
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, the 2nd, incoming laser beam, the 3rd, the BaGa after crystal aftertreatment and optics processing
2GeSe
6Non-linear optic crystal, the 4th, the outgoing laser beam that produces, the 5th, filter plate.
Fig. 2 is BaGa
2GeSe
6The structural representation of non-linear optic crystal.
Embodiment
Adopt BaSe+Ga
2Se
3+ GeSe
2=BaGa
2GeSe
6Reaction formula prepares BaGa with solid reaction process
2GeSe
6Compound;
Described BaSe is 4.326 grams, described Ga
2Se
3Be 7.527 grams, described GeSe
2Be 4.611 grams; Be BaSe: Ga
2Se
3: GeSe
2=0.02mol: 0.02mol: 0.02mol;
Concrete operation step is, takes by weighing respectively reagent by above-mentioned dosage in glove box, and they are put into mortar, mixes and carefully grinds, and in the silica tube of the Φ 12mm * 16mm that then packs into, is evacuated to 10
-3With oxyhydrogen flame the silica tube fusing is encapsulated behind the pa, put into retort furnace, slowly rise to 900 ℃, its temperature rise rate is 50 ℃/hour, and constant temperature 48 hours takes out after cooling, the taking-up sample is reground, place silica tube to vacuumize encapsulation, in 850 ℃ of sintering 24 hours, at this moment sample was shrunk to piece in retort furnace again; At this moment, with its taking-up, put into mortar and smash to pieces and grind to get Powdered BaGa
2GeSe
6Compound products.
Adopt BaSe+2Ga+Ge+5Se=BaGa
2GeSe
6Reaction formula prepares BaGa with solid reaction process
2GeSe
6Compound; Described BaSe is 4.326 grams, and described Ga is 2.789 grams, and described Ge is 1.452 grams, and described Se is 7.896 gram, i.e. BaSe: Ga: Ge: Se=0.02mol: 0.04mol: 0.02mol: 0.10mol;
Its concrete operation step is, takes by weighing respectively reagent by above-mentioned dosage in glove box, and they are put into mortar, mixes and carefully grinds, and in the silica tube of the Φ 12mm * 16mm that then packs into, is evacuated to 10
-3With flame the silica tube fusing is encapsulated behind the pa, put into retort furnace, slowly rise to 950 ℃, its temperature rise rate is 10 ℃/hour, and constant temperature 48 hours takes out after cooling, the taking-up sample is reground, place silica tube to vacuumize encapsulation, in 900 ℃ of sintering 24 hours, sample was shrunk to piece in retort furnace again; With its taking-up, put into mortar and smash to pieces to grind and to get the Powdered BaGa of preparation
2GeSe
6Compound products.
Adopt BaSe+Ga
2Se
3+ Ge+2Se=BaGa
2GeSe
6Reaction formula prepares BaGa with solid reaction process
2GeSe
6Compound; Described BaSe is 4.326 grams, described Ga
2Se
3Be 7.527 grams, described Ge is 1.452 grams, and described Se is 3.158 gram, i.e. BaSe: Ga
2Se
3: Ge: Se=0.02mol: 0.02mol: 0.02mol: 0.04mol;
Concrete operation step is, concrete operation step is, takes by weighing respectively reagent by above-mentioned dosage in glove box, and they are put into mortar, mixes and carefully grinds, and in the silica tube of the Φ 12mm * 16mm that then packs into, 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 30 ℃/hour, constant temperature 48 hours, take out after cooling, the taking-up sample is reground, and places silica tube to vacuumize encapsulation again, in retort furnace in 900 ℃ of sintering 24 hours, with its taking-up, put into mortar and smash to pieces and grind to get Powdered BaGa
2GeSe
6Compound products.
Adopt BaSe+2Ga+3Se+GeSe
2=BaGa
2GeSe
6Reaction formula prepares BaGa with solid reaction process
2GeSe
6Compound; Described BaSe is 4.326 grams, and described Ga is 2.789 grams, and described Se is 4.738 grams, described GeSe
2Be 4.611 gram, i.e. BaSe: Ga: Se: GeSe
2=0.02mol: 0.04mol: 0.06mol: 0.02mol;
Its concrete operation step is, takes by weighing respectively reagent by above-mentioned dosage in glove box, and they are put into mortar, mixes and carefully grinds, and in the silica tube of the Φ 12mm * 16mm that then packs into, 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, the taking-up sample is reground, and places silica tube to vacuumize encapsulation again, in retort furnace in 900 ℃ of sintering 24 hours, with its taking-up, put into mortar and smash to pieces to grind and to get the Powdered BaGa of preparation
2GeSe
6Compound products.
Embodiment 5, prepare Powdered BaGa
2GeSe
6Compound:
Adopt Ba+2Ga+Ge+6Se=BaGa
2GeSe
6Reaction formula prepares BaGa with solid reaction process
2GeSe
6Compound; Described Ba is 2.746 grams, and described Ga is 2.789 grams, and described Ge is 1.452 grams, and described Se is 9.475 gram, i.e. Ba: Ga: Ge: Se=0.02mol: 0.04mol: 0.02mol: 0.12mol;
Its concrete operation step is, takes by weighing respectively reagent by above-mentioned dosage in glove box, and they are put into mortar, mixes and carefully grinds, and in the silica tube of the Φ 12mm * 16mm that then packs into, is evacuated to 10
-3Behind the pa with flame with silica tube fusing encapsulation, put into retort furnace, slowly rise to 950 ℃, its temperature rise rate is 50 ℃/hour, constant temperature 48 hours takes out after cooling, puts into mortar and smashs to pieces to grind and to get the Powdered BaGa of preparation
2GeSe
6Compound products.
Embodiment 6, prepare Powdered BaGa
2GeSe
6Compound:
Adopt Ba+Se+Ga
2Se
3+ GeSe
2=BaGa
2GeSe
6Reaction formula prepares BaGa with solid reaction process
2GeSe
6Compound; Described Ba is 2.746 grams, described Ga
2Se
3Be 7.527 grams, described GeSe
2Be 4.611 grams, described Se is 1.579 gram, i.e. Ba: Ga
2Se
3: GeSe
2: Se=0.02mol: 0.02mol: 0.02mol: 0.02mol;
Its concrete operation step is, takes by weighing respectively reagent by above-mentioned dosage in glove box, and they are put into mortar, mixes and carefully grinds, and in the silica tube of the Φ 12mm * 16mm that then packs into, is evacuated to 10
-3Behind the pa with flame with silica tube fusing encapsulation, put into retort furnace, slowly rise to 950 ℃, its temperature rise rate is 30 ℃/hour, constant temperature 48 hours takes out after cooling, puts into mortar and smashs to pieces to grind and to get the Powdered BaGa of preparation
2GeSe
6Compound products.
Embodiment 7, prepare Powdered BaGa
2GeSe
6Compound:
Adopt Ba+4Se+2Ga+GeSe
2=BaGa
2GeSe
6Reaction formula prepares BaGa with solid reaction process
2GeSe
6Compound; Described Ba is 2.746 grams, and described Ga is 2.789 grams, described GeSe
2Be 4.611 grams, described Se is 6.317 gram, i.e. Ba: Ga: GeSe
2: Se=0.02mol: 0.04mol: 0.02mol: 0.08mol;
Its concrete operation step is, takes by weighing respectively reagent by above-mentioned dosage in glove box, and they are put into mortar, mixes and carefully grinds, and in the silica tube of the Φ 12mm * 16mm that then packs into, is evacuated to 10
-3Behind the pa with flame with silica tube fusing encapsulation, put into retort furnace, slowly rise to 950 ℃, its temperature rise rate is 30 ℃/hour, constant temperature 48 hours takes out after cooling, puts into mortar and smashs to pieces to grind and to get the Powdered BaGa of preparation
2GeSe
6Compound products.
Embodiment 8, prepare Powdered BaGa
2GeSe
6Compound:
Adopt Ba+3Se+Ga
2Se
3+ Ge=BaGa
2GeSe
6Reaction formula prepares BaGa with solid reaction process
2GeSe
6Compound; Described Ba is 2.746 grams, described Ga
2Se
3Be 7.527 grams, described Ge is 1.452 grams, and described Se is 4.738 gram, i.e. Ba: Ga
2Se
3: Ge: Se=0.02mol: 0.02mol: 0.02mol: 0.06mol;
Its concrete operation step is, takes by weighing respectively reagent by above-mentioned dosage in glove box, and they are put into mortar, mixes and carefully grinds, and in the silica tube of the Φ 12mm * 16mm that then packs into, is evacuated to 10
-3Behind the pa with flame with silica tube fusing encapsulation, put into retort furnace, slowly rise to 950 ℃, its temperature rise rate is 10 ℃/hour, constant temperature 48 hours takes out after cooling, puts into mortar and smashs to pieces to grind and to get the Powdered BaGa of preparation
2GeSe
6Compound products.
Embodiment 9, adopt the standby BaGa of high-temperature fusant spontaneous crystallization legal system
2GeSe
6Crystal:
With the BaGa that obtains among the embodiment 1 to 8
2GeSe
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 980 ℃, constant temperature 72 hours to room temperature, is closed the tubular type growth furnace with the speed slow cooling of 3-5 ℃/h; After the silica tube cooling, cut, can obtain red transparent BaGa
2GeSe
6Crystal.
Embodiment 10, adopt falling crucible method to prepare BaGa
2GeSe
6Crystal:
With the BaGa that obtains among the embodiment 1 to 8
2GeSe
6Powder is packed in the quartz glass tube of Φ 15mm * 18mm, is evacuated to 10
-3Behind the handkerchief, be placed in the crystal growing furnace with oxyhydrogen flame encapsulation, slowly rise to 980 ℃ raw material is melted fully after, growing apparatus vertically descends with 0.1-1.0mm/ hour speed; After the crystal growth finished, growing apparatus was down to room temperature with 30 hours, obtained red transparent BaGa
2GeSe
6Crystal.
After tested, the prepared BaGa of above-described embodiment 9-10
2GeSe
6Non-linear optic crystal belongs to trigonal system, and spacer is R3, and its unit cell parameters is: a=b=10.008 (1)
C=9.090 (2)
α=β=90 °, γ=120 °, Z=3, V=788.4
Has frequency-doubled effect; Fig. 2 is this BaGa
2GeSe
6The structural representation of non-linear optic crystal.
Embodiment 11:
BaGa with embodiment 9 and 10 gained
2GeSe
6Crystal is done to see through spectrometry, and this crystal is transparent in 0.59 μ m-18 mum wavelength scope; Not easily broken, be easy to cutting, polishing and preservation, not deliquescence; BaGa with embodiment 9 and 10 gained
2GeSe
6Crystal is placed on accompanying drawing 1 shown device label and is 3 position, at room temperature, makes light source with the Ho:Tm:Cr:YAG laser apparatus of transferring Q, and 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 is to adopt BaGa of the present invention
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, the 2nd, incoming laser beam, the 3rd, the BaGa after crystal aftertreatment and optics processing
2GeSe
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 BaGa
2GeSe
6Single crystal 3, the outgoing laser beam 4 that produces passes through filter plate 5, and obtains needed laser beam;
Use BaGa of the present invention
2GeSe
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, and concerning Ho:Tm:Cr:YAG laser apparatus that use to transfer Q was made the frequency doubling device of light source, incoming beam 2 was that wavelength is the infrared light of 2090nm, passes through BaGa
2GeSe
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 BaGa
2GeSe
6Compound.
2. described BaGa of claim 1
2GeSe
6The preparation method of compound, its step is as follows:
To contain the Ba material, contain the Ga material, contain Ge material and simple substance Se according to mol ratio Ba: Ga: Ge: Se=1: 2: 1: 6 ratio batching and mix after, be heated to 850-950 ℃ and carry out solid state reaction, obtaining chemical formula is BaGa
2GeSe
6Compound; The described Ba of containing material is barium simple substance or barium selenide; The described Ge of containing material is germanium simple substance or two Germanium selenide; The described Ga of containing material is gallium simple substance or three selenizings, two galliums.
3. by the described BaGa of claim 2
2GeSe
6The preparation method of compound is characterized in that, solid state reaction is carried out in described heating, and to obtain chemical formula be BaGa
2GeSe
6The step of compound be: pack into after above-mentioned batching is ground in the silica tube, silica tube be evacuated to 10
-3Pa also melts encapsulation, puts into retort furnace, is warming up to 850-950 ℃ with 10-50 ℃/hour speed, and constant temperature 48 hours takes out sample after cooling; The sample that takes out is reground places again silica tube to be evacuated to 10
-3Pa also melts encapsulation, puts into retort furnace again and is warming up to 850-950 ℃ of sintering 24 hours; Sample is taken out, and smash to pieces and grind to get Powdered BaGa
2GeSe
6Compound.
4. BaGa
2GeSe
6Non-linear optic crystal, this BaGa
2GeSe
6Non-linear optic crystal does not have symmetry centre, belongs to trigonal system, and spacer is R3, and its unit cell parameters is: a=b=10.008 (1)
C=9.090 (2)
α=β=90 °, γ=120 °, Z=3, V=788.4
5. described BaGa of claim 4
2GeSe
6The preparation method of non-linear optic crystal, it is high-temperature fusant spontaneous crystallization method growth BaGa
2GeSe
6Non-linear optic crystal the steps include: Powdered BaGa
2GeSe
6Compound be heated to melt high temperature solution and keep 48-96 hour after, be cooled to room temperature with 3-5 ℃/hour rate of temperature fall, obtain red transparent BaGa
2GeSe
6Crystal.
6. by the described BaGa of claim 5
2GeSe
6The preparation method of non-linear optic crystal is characterized in that, described Powdered BaGa
2GeSe
6Being prepared as follows of compound:
To contain the Ba material, contain the Ga material, contain Ge material and simple substance Se according to mol ratio Ba: Ga: Ge: Se=1: after 2: 1: 6 ratio mixed, solid state reaction was carried out in heating, and obtaining chemical formula is BaGa
2GeSe
6Compound, grind to get Powdered BaGa through smashing to pieces
2GeSe
6Compound; The described Ba of containing material is barium simple substance or barium selenide; The described Ge of containing material is germanium simple substance or two Germanium selenide; The described Ga of containing material is gallium simple substance or three selenizings, two galliums.
7. described BaGa of claim 4
2GeSe
6The preparation method of non-linear optic crystal, it is Bridgman-Stockbarge method for growing BaGa
2GeSe
6Non-linear optic crystal, its step comprises:
With BaGa
2GeSe
6Powder is put into crystal growing apparatus, slowly is warming up to powder smelting, and after powder melted fully, crystal growing apparatus vertically descended with the speed of 0.1-1.0mm/h, carries out BaGa in crystal growing apparatus decline process
2GeSe
6The non-linear optic crystal growth, its growth cycle is 10-20 days.
8. by the described BaGa of claim 7
2GeSe
6The preparation method of non-linear optic crystal is characterized in that, its step also comprises BaGa
2GeSe
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 the speed that is not more than 30～100 ℃/hour.
9. BaGa claimed in claim 4
2GeSe
6The purposes of non-linear optic crystal is characterized in that, this BaGa
2GeSe
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 this BaGa
2GeSe
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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