CN102976287B - 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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- CN102976287B CN102976287B CN201110258297.8A CN201110258297A CN102976287B CN 102976287 B CN102976287 B CN 102976287B CN 201110258297 A CN201110258297 A CN 201110258297A CN 102976287 B CN102976287 B CN 102976287B
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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 20
- 238000000034 method Methods 0.000 claims abstract description 9
- 150000001875 compounds Chemical class 0.000 claims abstract description 7
- 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
- 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 26
- 238000005538 encapsulation Methods 0.000 claims description 14
- 238000001816 cooling Methods 0.000 claims description 11
- 239000000155 melt Substances 0.000 claims description 6
- 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
- 238000010438 heat treatment Methods 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
- 238000002156 mixing Methods 0.000 claims 1
- 239000000203 mixture Substances 0.000 claims 1
- 238000004519 manufacturing process Methods 0.000 abstract description 2
- 238000005336 cracking Methods 0.000 abstract 1
- 238000003860 storage Methods 0.000 abstract 1
- 229910005866 GeSe Inorganic materials 0.000 description 36
- 238000006243 chemical reaction Methods 0.000 description 18
- 239000004570 mortar (masonry) Substances 0.000 description 16
- 239000007787 solid Substances 0.000 description 10
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- 238000004321 preservation Methods 0.000 description 3
- 229910019655 synthetic inorganic crystalline material Inorganic materials 0.000 description 3
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- 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
- 230000008025 crystallization Effects 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 230000006378 damage Effects 0.000 description 1
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- 230000008030 elimination Effects 0.000 description 1
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- 230000005693 optoelectronics Effects 0.000 description 1
- 230000010355 oscillation Effects 0.000 description 1
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- 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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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 for the purposes of the device for non-linear optical made.
Background technology
The 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 without symmetry centre just may have non-linear optical effect.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 meet the requirement of practical 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, as AgGaQ
2(Q=S, Se, Te), the light injury threshold of infrared non-linear crystal is too low and crystal growth is difficult, has directly affected actual use.Middle-infrared band non-linear optic crystal has important application at optoelectronic areas, such as it, can the laser of near-infrared band (as 1.064 μ m) be extended to middle infrared 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 finding 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 object 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:
By containing Ba material, containing Ga material, containing Ge material and simple substance Se according to mol ratio Ba: Ga: Ge: Se=1: after the ratio of 2: 1: 6 is prepared burden and mixed, 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); Described is barium simple substance or barium selenide containing Ba material; Described is germanium simple substance or two Germanium selenide containing Ge material; Described is gallium simple substance or three selenizing two galliums containing Ga material.
The step that solid state reaction is carried out in described heating is: after above-mentioned batching is ground, pack in silica tube, silica tube is evacuated to 10
-3pa also melts encapsulation, puts into retort furnace, with the speed of 10-50 ℃/h, is warming up to 850-950 ℃, and constant temperature 48 hours, takes out sample after cooling; The sample taking out is reground and is placed in silica tube again and is evacuated to 10
-3pa also melts encapsulation, then puts into retort furnace and be warming up to 850-950 ℃ of sintering 24 hours; Sample is taken out and smashed to pieces and grind to obtain Powdered BaGa
2geSe
6compound.
Described BaGa
2geSe
6compound can be prepared 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 is heated to melt to obtain high temperature solution keep, after 48-96 hour, being cooled to room temperature with the rate of temperature fall of 3-5 ℃/h, obtains red transparent BaGa
2geSe
6crystal.
Described Powdered BaGa
2geSe
6being prepared as follows of compound:
By containing Ba material, containing Ga material, containing Ge material and simple substance Se according to mol ratio Ba: Ga: Ge: Se=1: after the ratio of 2: 1: 6 is prepared burden and mixed, 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); Described is barium simple substance or barium selenide containing Ba material; Described is germanium simple substance or two Germanium selenide containing Ge material; Described is gallium simple substance or three selenizing two galliums containing Ga material.
BaGa of the present invention
2geSe
6compound can be prepared 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
6a preparation method again of non-linear optic crystal, it is Bridgman-Stockbarge method for growing BaGa
2geSe
6non-linear optic crystal, its step is as follows:
By Powdered BaGa
2geSe
6compound is put into crystal growing apparatus, is slowly warming up to its fusing, and after it melts completely, crystal growing apparatus vertically declines with the speed of 0.1-1.0mm/h, in crystal growing apparatus decline process, carries out BaGa
2geSe
6non-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 growth furnace and anneal, be cooled to room temperature (preferably rate of temperature fall is 30～50 ℃/h) to be not more than the speed of 30～100 ℃/h.
Adopt above-mentioned two kinds of methods all can obtain the BaGa that is of a size of centimetre-sized
2geSe
6non-linear optic crystal; Use large size crucible, and extend vegetative period, can obtain corresponding large-size BaGa
2geSe
6non-linear optic crystal.
According to the crystallography data of crystal, crystal blank is directed, by required angle, thickness and sectional dimension sliced crystal, by the logical light mirror polish of crystal, can be used as device for non-linear optical and use, this BaGa
2geSe
6it is stable that non-linear optic crystal has physical and chemical performance, 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 at least a branch of incidence electromagnetic radiation by least one this BaGa
2geSe
6after non-linear optic crystal, produce the device that at least a branch of frequency is different from the output radiation of incidence electromagnetic radiation.
BaGa of the present invention
2geSe
6compound, the non-linear optic crystal of this compound and its production and use there is following effect:
At this BaGa
2geSe
6the growing crystals of non-linear optic crystal is easily grown up and transparent nothing parcel, has the speed of growth very fast, and growth temperature is low, and cost is low, easily obtains the advantages such as large-size crystal; The BaGa obtaining
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.
Accompanying drawing explanation
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 producing, the 5th, filter plate.
Fig. 2 is BaGa
2geSe
6the structural representation of non-linear optic crystal.
Embodiment
Embodiment 1, prepares Powdered BaGa
2geSe
6compound:
Adopt BaSe+Ga
2se
3+ GeSe
2=BaGa
2geSe
6reaction formula is prepared BaGa with solid reaction process
2geSe
6compound;
Described BaSe is 4.326 grams, described Ga
2se
3be 7.527 grams, described GeSe
2it is 4.611 grams; Be BaSe: Ga
2se
3: GeSe
2=0.02mol: 0.02mol: 0.02mol;
Concrete operation step is, in glove box, by above-mentioned dosage, takes respectively reagent, and they are put into mortar, mixes and carefully grinds, and then packs in the silica tube of Φ 12mm * 16mm, is evacuated to 10
-3after pa, with oxyhydrogen flame, silica tube fusing is encapsulated, put into retort furnace, slowly rise to 900 ℃, its temperature rise rate is 50 ℃/h, and 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, in 850 ℃ of sintering 24 hours, at this moment sample was shrunk to piece; Now, taken out, put into mortar and smash to pieces and grind to obtain Powdered BaGa
2geSe
6compound products.
Embodiment 2, prepare Powdered BaGa
2geSe
6compound:
Adopt BaSe+2Ga+Ge+5Se=BaGa
2geSe
6reaction formula is prepared 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 grams, i.e. BaSe: Ga: Ge: Se=0.02mol: 0.04mol: 0.02mol: 0.10mol;
Its concrete operation step is, in glove box, by above-mentioned dosage, takes respectively reagent, and they are put into mortar, mixes and carefully grinds, and then packs in the silica tube of Φ 12mm * 16mm, is evacuated to 10
-3after pa, with flame, silica tube fusing is encapsulated, put into retort furnace, slowly rise to 950 ℃, its temperature rise rate is 10 ℃/h, and 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, in 900 ℃ of sintering 24 hours, sample was shrunk to piece; Taken out, put into mortar and smash to pieces to grind and to obtain the Powdered BaGa of preparation
2geSe
6compound products.
Embodiment 3, prepare Powdered BaGa
2geSe
6compound:
Adopt BaSe+Ga
2se
3+ Ge+2Se=BaGa
2geSe
6; Reaction formula is prepared 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 grams, i.e. BaSe: Ga
2se
3: Ge: Se=0.02mol: 0.02mol: 0.02mol: 0.04mol;
Concrete operation step is, concrete operation step is, in glove box, by above-mentioned dosage, takes respectively reagent, and they are put into mortar, mixes and carefully grinds, and then packs in the silica tube of Φ 12mm * 16mm, is evacuated to 10
-3after pa, with flame, silica tube fusing is encapsulated, put into retort furnace, slowly rise to 900 ℃, its temperature rise rate is 30 ℃/h, constant temperature 48 hours, take out after cooling, taking-up sample is reground, then is placed in silica tube and vacuumizes encapsulation, in retort furnace in 900 ℃ of sintering 24 hours, taken out, put into mortar and smash to pieces and grind to obtain Powdered BaGa
2geSe
6compound products.
Embodiment 4, prepare Powdered BaGa
2geSe
6compound:
Adopt BaSe+2Ga+3Se+GeSe
2=BaGa
2geSe
6reaction formula is prepared 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 grams, i.e. BaSe: Ga: Se: GeSe
2=0.02mol: 0.04mol: 0.06mol: 0.02mol;
Its concrete operation step is, in glove box, by above-mentioned dosage, takes respectively reagent, and they are put into mortar, mixes and carefully grinds, and then packs in the silica tube of Φ 12mm * 16mm, is evacuated to 10
-3after pa, with flame, silica tube fusing is encapsulated, put into retort furnace, slowly rise to 900 ℃, its temperature rise rate is 10 ℃/h, constant temperature 48 hours, take out after cooling, taking-up sample is reground, then is placed in silica tube and vacuumizes encapsulation, in retort furnace in 900 ℃ of sintering 24 hours, taken out, put into mortar and smash to pieces to grind and to obtain the Powdered BaGa of preparation
2geSe
6compound products.
Embodiment 5, prepare Powdered BaGa
2geSe
6compound:
Adopt Ba+2Ga+Ge+6Se=BaGa
2geSe
6reaction formula is prepared 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 grams, i.e. Ba: Ga: Ge: Se=0.02mol: 0.04mol: 0.02mol: 0.12mol;
Its concrete operation step is, in glove box, by above-mentioned dosage, takes respectively reagent, and they are put into mortar, mixes and carefully grinds, and then packs 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 950 ℃, its temperature rise rate is 50 ℃/h, constant temperature 48 hours takes out after cooling, puts into mortar and smashs to pieces to grind and to obtain 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 is prepared 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 grams, i.e. Ba: Ga
2se
3: GeSe
2: Se=0.02mol: 0.02mol: 0.02mol: 0.02mol;
Its concrete operation step is, in glove box, by above-mentioned dosage, takes respectively reagent, and they are put into mortar, mixes and carefully grinds, and then packs 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 950 ℃, its temperature rise rate is 30 ℃/h, constant temperature 48 hours takes out after cooling, puts into mortar and smashs to pieces to grind and to obtain 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 is prepared 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 grams, i.e. Ba: Ga: GeSe
2: Se=0.02mol: 0.04mol: 0.02mol: 0.08mol;
Its concrete operation step is, in glove box, by above-mentioned dosage, takes respectively reagent, and they are put into mortar, mixes and carefully grinds, and then packs 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 950 ℃, its temperature rise rate is 30 ℃/h, constant temperature 48 hours takes out after cooling, puts into mortar and smashs to pieces to grind and to obtain 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 is prepared 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 grams, i.e. Ba: Ga
2se
3: Ge: Se=0.02mol: 0.02mol: 0.02mol: 0.06mol;
Its concrete operation step is, in glove box, by above-mentioned dosage, takes respectively reagent, and they are put into mortar, mixes and carefully grinds, and then packs 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 950 ℃, its temperature rise rate is 10 ℃/h, constant temperature 48 hours takes out after cooling, puts into mortar and smashs to pieces to grind and to obtain the Powdered BaGa of preparation
2geSe
6compound products.
Embodiment 9, adopt high-temperature fusant spontaneous crystallization legal system for BaGa
2geSe
6crystal:
By the BaGa obtaining in embodiment 1 to 8
2geSe
6powder packs in the quartz glass tube of Φ 12mm * 16mm, is evacuated to 10
-3after handkerchief, with oxyhydrogen flame encapsulation, be placed in tubular type growth furnace, slowly rise to 980 ℃, constant temperature 72 hours, to room temperature, closes tubular type growth furnace with the speed slow cooling of 3-5 ℃/h; After silica tube is cooling, cut, can obtain red transparent BaGa
2geSe
6crystal.
Embodiment 10, adopt falling crucible method to prepare BaGa
2geSe
6crystal:
By the BaGa obtaining in embodiment 1 to 8
2geSe
6powder packs 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 980 ℃ raw material is melted completely after, growing apparatus vertically declines with the speed of 0.1-1.0mm/ hour; After crystal growth finishes, 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
there is frequency-doubled effect; Fig. 2 is this BaGa
2geSe
6the structural representation of non-linear optic crystal.
Embodiment 11:
By the BaGa of embodiment 9 and 10 gained
2geSe
6crystal is done to see through spectrometry, and this crystal is transparent within the scope of 0.59 μ m-18 mum wavelength; Not easily broken, be easy to cutting, polishing and preservation, not deliquescence; By the BaGa of embodiment 9 and 10 gained
2geSe
6crystal, is placed on the position that accompanying drawing 1 shown device label is 3, at room temperature, and with adjusting the Ho:Tm:Cr:YAG laser apparatus of Q to make light source, the infrared light that incident wavelength is 2090nm, the frequency doubled light that output wavelength is 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 producing, the 5th, filter plate; By laser apparatus 1, send incoming laser beam 2 and inject BaGa
2geSe
6single crystal 3, the outgoing laser beam 4 producing 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 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 use adjusting the Ho:Tm:Cr:YAG laser apparatus of Q to do the frequency doubling device of light source, incoming beam 2 is that wavelength is the infrared light of 2090nm, passes through BaGa
2geSe
6non-linear optic crystal produces the frequency doubled light that wavelength is 1045, 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 (7)
1. a BaGa
2geSe
6the preparation method of compound, its step is as follows:
After preparing burden according to the ratio of mol ratio Ba:Ga:Ge:Se=1:2:1:6 and mix containing Ba material, containing Ga material, containing Ge material and simple substance Se, be heated to 850-950 ℃ and carry out solid state reaction, obtaining chemical formula is BaGa
2geSe
6compound; Described is barium simple substance or barium selenide containing Ba material; Described is germanium simple substance or two Germanium selenide containing Ge material; Described is gallium simple substance or three selenizing two galliums containing Ga material;
Solid state reaction is carried out in described heating, and to obtain chemical formula be BaGa
2geSe
6the step of compound be: after above-mentioned batching is ground, pack in silica tube, silica tube be evacuated to 10
-3pa also melts encapsulation, puts into retort furnace, with the speed of 10-50 ℃/h, is warming up to 850-950 ℃, and constant temperature 48 hours, takes out sample after cooling; The sample taking out is reground and is placed in silica tube again and is evacuated to 10
-3pa also melts encapsulation, then puts into retort furnace and be warming up to 850-950 ℃ of sintering 24 hours; Sample is taken out, and smash to pieces and grind to obtain Powdered BaGa
2geSe
6compound.
2. a 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:
α=β=90 °, γ=120 °, Z=3,
3. BaGa described in a claim 2
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 is heated to melt to obtain high temperature solution keep, after 48-96 hour, being cooled to room temperature with the rate of temperature fall of 3-5 ℃/h, obtains red transparent BaGa
2geSe
6crystal.
4. by BaGa described in claim 3
2geSe
6the preparation method of non-linear optic crystal, is characterized in that, described Powdered BaGa
2geSe
6being prepared as follows of compound:
After mixing according to the ratio of mol ratio Ba:Ga:Ge:Se=1:2:1:6 containing Ba material, containing Ga material, containing Ge material and simple substance Se, solid state reaction is carried out in heating, and obtaining chemical formula is BaGa
2geSe
6compound, through smashing to pieces, grind to obtain Powdered BaGa
2geSe
6compound; Described is barium simple substance or barium selenide containing Ba material; Described is germanium simple substance or two Germanium selenide containing Ge material; Described is gallium simple substance or three selenizing two galliums containing Ga material.
5. BaGa described in a claim 2
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:
By BaGa
2geSe
6powder is put 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, carries out BaGa
2geSe
6non-linear optic crystal growth, its growth cycle is 10-20 days.
6. by BaGa described in claim 5
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 growth furnace and anneal, be cooled to room temperature to be not more than the speed of 30～100 ℃/h.
7. a BaGa claimed in claim 2
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 at least a branch of incidence electromagnetic radiation by least one this BaGa
2geSe
6after non-linear optic crystal, produce the device that at least a branch of frequency is different from the output radiation of incidence electromagnetic radiation.
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