CN101767778B - BaGa4Se7Compound and BaGa4Se7Nonlinear optical crystal and its preparation method and use - Google Patents
BaGa4Se7Compound and BaGa4Se7Nonlinear optical crystal and its preparation method and use Download PDFInfo
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- CN101767778B CN101767778B CN2010191140499A CN201019114049A CN101767778B CN 101767778 B CN101767778 B CN 101767778B CN 2010191140499 A CN2010191140499 A CN 2010191140499A CN 201019114049 A CN201019114049 A CN 201019114049A CN 101767778 B CN101767778 B CN 101767778B
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- 239000013078 crystal Substances 0.000 title claims abstract description 103
- 230000003287 optical effect Effects 0.000 title claims abstract description 28
- 238000002360 preparation method Methods 0.000 title claims abstract description 17
- 238000000034 method Methods 0.000 claims abstract description 12
- 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 38
- 239000000126 substance Substances 0.000 claims description 28
- 239000000463 material Substances 0.000 claims description 27
- 239000000377 silicon dioxide Substances 0.000 claims description 17
- 238000005538 encapsulation Methods 0.000 claims description 11
- 239000002994 raw material Substances 0.000 claims description 11
- 238000002156 mixing Methods 0.000 claims description 8
- 238000001816 cooling Methods 0.000 claims description 7
- 239000000155 melt Substances 0.000 claims description 7
- 229910052788 barium Inorganic materials 0.000 claims description 6
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 claims description 6
- RJWLRCHYHHXJLX-UHFFFAOYSA-N barium(2+);selenium(2-) Chemical compound [Se-2].[Ba+2] RJWLRCHYHHXJLX-UHFFFAOYSA-N 0.000 claims description 6
- 238000010671 solid-state reaction Methods 0.000 claims description 6
- 238000010792 warming Methods 0.000 claims description 6
- 238000005245 sintering Methods 0.000 claims description 5
- 230000005670 electromagnetic radiation Effects 0.000 claims description 4
- 238000007716 flux method Methods 0.000 claims description 3
- 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
- GYHNNYVSQQEPJS-UHFFFAOYSA-N Gallium Chemical compound [Ga] GYHNNYVSQQEPJS-UHFFFAOYSA-N 0.000 claims 3
- 229910052733 gallium Inorganic materials 0.000 claims 3
- 238000012545 processing Methods 0.000 abstract description 6
- 238000004519 manufacturing process Methods 0.000 abstract description 2
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- 238000003860 storage Methods 0.000 abstract 1
- 238000006243 chemical reaction Methods 0.000 description 10
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- 239000007787 solid Substances 0.000 description 5
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- 239000003153 chemical reaction reagent Substances 0.000 description 3
- 238000000227 grinding Methods 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 238000004321 preservation Methods 0.000 description 3
- 238000009331 sowing Methods 0.000 description 3
- 229910019655 synthetic inorganic crystalline material Inorganic materials 0.000 description 3
- 230000003321 amplification Effects 0.000 description 2
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- 238000003199 nucleic acid amplification method Methods 0.000 description 2
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- 238000005303 weighing 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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Abstract
The present invention relates to BaGa4Se7Compound and BaGa4Se7Nonlinear optical crystal and its preparation method and application; the BaGa4Se7The compound is prepared by adopting a solid-phase reaction; BaGa4Se7The nonlinear optical crystal is grown by a high-temperature melt spontaneous crystallization method, a fluxing agent method or a Bridgman method; in the BaGa4Se7The 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 BaGa4Se7The 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 BaGa4Se7The nonlinear optical crystal can be used for manufacturing nonlinear optical devices.
Description
Technical field
The present invention relates to a kind of BaGa
4Se
7Compound, BaGa
4Se
7Non-linear optic crystal (BaGa
4Se
7Monocrystalline) and this BaGa
4Se
7The preparation method of monocrystalline and this BaGa
4Se
7The purposes of the device for non-linear optical that monocrystalline is used to make.
Background technology
Crystal with non-linear optical effect is called non-linear optic crystal.Here non-linear optical effect is meant effects such as frequency multiplication and frequency, difference frequency, parameter amplification.Have only crystal just to have non-linear optical effect with symmetry centre.Utilize the crystalline non-linear optical effect, can process second harmonic generator, upper and lower frequency converter, device for non-linear optical such as optical parametric oscillator.The laser that laser apparatus produces can carry out frequency inverted through device for non-linear optical, thereby obtains the laser of more how useful wavelength, and laser apparatus is more widely used.According to the difference of material application band, can be divided into ultraviolet region, visible and near-infrared region and mid-infrared light district nonlinear optical material three major types.The non-linear optical crystal material of visible region and ultraviolet region can satisfy requirement of actual application; Like 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 like AgGaQ
2(Te), the light injury threshold of infrared non-linear crystal is too low difficult with crystal growth, has directly influenced actual use for Q=S, Se.The middle-infrared band non-linear optic crystal has important use at optoelectronic areas, and for example it can extend to middle infrared with the laser (like 1.064 μ m) of near-infrared band through means such as optical parametric oscillation or optical parameter amplifications; Also can be to the important laser in mid-infrared light district (like 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 difficult point and forward position direction of current nonlinear optical material research field.
Summary of the invention
It is BaGa that the object of the invention is to provide a kind of chemical formula
4Se
7Compound.
Another purpose of the present invention is to provide a kind of BaGa
4Se
7Non-linear optic crystal.
Still a further object of the present invention is to provide BaGa
4Se
7The preparation method of non-linear optic crystal.
A further object of the invention is to provide BaGa
4Se
7The purposes of non-linear optic crystal.
Technical scheme of the present invention is following:
It is BaGa that the present invention provides a kind of chemical formula
4Se
7Compound.
BaGa provided by the invention
4Se
7The preparation method of compound, its step is following:
With Ba source material, Ga source material and simple substance Se according to mol ratio Ba: Ga: Se=1: 4: 7 ratio batching and mix after, be heated to 800-950 ℃ and carry out solid state reaction and (in principle, adopt general chemical synthesis process can prepare BaGa
4Se
7Compound; The preferred solid reaction process of the present invention), obtaining chemical formula is BaGa
4Se
7Compound;
Said Ba source material is barium simple substance or barium selenide;
Said Ga source material is for sowing simple substance or three selenizings two are sowed.
The step that solid state reaction is carried out in said heating is: pack into after above-mentioned batching is ground in the silica tube, silica tube is evacuated to 10
-3Pa also melts encapsulation, puts into retort furnace, is warming up to 800-950 ℃ with 10-50 ℃/hour speed, and constant temperature 48 hours takes out sample after cooling; The sample that takes out is ground mixing again places silica tube to be evacuated to 10 again
-3Pa also melts encapsulation, puts into retort furnace again and is warming up to 800-950 ℃ of sintering 24 hours; Sample is taken out, and smash to pieces grind Powdered BaGa
4Se
7Compound.
Said BaGa
4Se
7Compound can prepare by following reaction formula:
(1)Ba+4Ga+7Se＝BaGa
4Se
7；
(2)BaSe+4Ga+6Se＝BaGa
4Se
7；
(3)Ba+Se+2Ga
2Se
3＝BaGa
4Se
7；
(4)BaSe+2Ga
2Se
3＝BaGa
4Se
7。
BaGa provided by the invention
4Se
7Non-linear optic crystal, this BaGa
4Se
7Non-linear optic crystal does not possess has symmetry centre, belongs to oblique system, and spacer is Pc, and its unit cell parameters is:
α=γ=90 °, β=121.24 (2) °.
BaGa provided by the invention
4Se
7The preparation method of non-linear optic crystal, it is high-temperature fusant spontaneous crystallization method growth BaGa
4Se
7Non-linear optic crystal the steps include: Powdered BaGa
4Se
7Compound be heated to melt high temperature solution and keep 24-96 hour after, be cooled to room temperature with 1-10 ℃/hour rate of temperature fall, obtain the BaGa of yellow transparent
4Se
7Crystal.
Said Powdered BaGa
4Se
7The preparation of compound is following:
With Ba source material, Ga source material and simple substance Se according to mol ratio Ba: Ga: Se=1: 4: 7 mixed evenly after, be heated to 800-950 ℃ and carry out solid state reaction and (in principle, adopt general chemical synthesis process can prepare BaGa
4Se
7Compound; The preferred solid reaction process of the present invention), obtaining chemical formula is BaGa
4Se
7Compound, through smash to pieces grind Powdered BaGa
4Se
7Compound;
Said Ba source material is barium simple substance or barium selenide;
Said Ga source material is for sowing simple substance or three selenizings two are sowed.
Said BaGa
4Se
7Compound can prepare by following reaction formula:
(1)Ba+4Ga+7Se＝BaGa
4Se
7；
(2)BaSe+4Ga+6Se＝BaGa
4Se
7；
(3)Ba+Se+2Ga
2Se
3＝BaGa
4Se
7；
(4)BaSe+2Ga
2Se
3＝BaGa
4Se
7。
BaGa provided by the invention
4Se
7Another preparation method of non-linear optic crystal, it is flux method growth BaGa
4Se
7Non-linear optic crystal, its step is following:
With BaGa
4Se
7Compound and fusing assistant are 1 in mass parts: the ratio batching of 0.5-5, be heated to 750-900 ℃ and constant temperature 2-6 days, and reduce to room temperature with 1-10 ℃/hour rate of temperature fall then, obtain the BaGa of yellow transparent
4Se
7Crystal;
Said fusing assistant is KCl, KBr or Li
2Se.
BaGa provided by the invention
4Se
7A preparation method again of non-linear optic crystal, it is Bridgman-Stockbarge method for growing BaGa
4Se
7Non-linear optic crystal, its step is following:
To contain the Ba raw material, contain the Ga raw material and simple substance Se simple substance is put into crystal growing apparatus, slowly be warming up to the raw material fusing, treat that raw material melts fully after, crystal growing apparatus vertically descends with the speed of 0.1-10mm/h, in crystal growing apparatus decline process, carries out BaGa
4Se
7The non-linear optic crystal growth, its growth cycle is 5-20 days;
Said Ba source material is barium simple substance or barium selenide;
Said Ga source material is for sowing simple substance or three selenizings two are sowed.
Bridgman-Stockbarge method for growing BaGa of the present invention
4Se
7Non-linear optic crystal also comprises BaGa
4Se
7The aftertreatment of non-linear optic crystal: after crystal growth finishes, will crystal stay in the reactors 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 three kinds of methods all can obtain to be of a size of millimetre-sized BaGa
4Se
7Non-linear optic crystal; Use the large size crucible, and prolong vegetative period, then can obtain corresponding large-size BaGa
4Se
7Non-linear optic crystal.
According to crystalline crystallography data, the crystal blank is directed, by required angle, thickness and sectional dimension sliced crystal,, promptly can be used as device for non-linear optical and use this BaGa the logical light mirror polish of crystal
4Se
7Non-linear optic crystal has physical and chemical performance to be stablized, and hardness is bigger, and good mechanical property is not easily broken, is difficult for deliquescence, is easy to advantages such as processing and preservation; So the present invention also further provides BaGa
4Se
7The purposes of non-linear optic crystal, this BaGa
4Se
7Non-linear optic crystal is used to prepare device for non-linear optical, and this device for non-linear optical comprises a branch of at least incidence electromagnetic radiation through at least one this BaGa
4Se
7Produce 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
4Se
7Compound, this compound non-linear optic crystal and its production and use have a following effect:
At this BaGa
4Se
7The growing crystals of non-linear optic crystal is prone to grow up and transparent nothing parcel, and it is very fast to have the speed of growth, and cost is low, obtains advantages such as large-size crystal easily; The BaGa that is obtained
4Se
7Non-linear optic crystal has the transmission region than broad, and hardness is bigger, good mechanical property, and not easily broken and deliquescence is easy to advantages such as processing and preservation; This BaGa
4Se
7Non-linear optic crystal can be used for making device for non-linear optical.
Description of drawings
Fig. 1 adopts BaGa of the present invention
4Se
7The fundamental diagram of a kind of typical nonlinear optics that non-linear optic crystal is processed, wherein 1 is laser apparatus, the 2nd, incoming laser beam, the 3rd, the BaGa after crystal aftertreatment and optics processing
4Se
7Non-linear optic crystal, the 4th, the outgoing laser beam that is produced, the 5th, filter plate.
Fig. 2 is BaGa
4Se
7The structural representation of non-linear optic crystal.
Embodiment
Adopt BaSe+2Ga
2Se
3=BaGa4Se reaction formula prepares BaGa with solid reaction process
4Se
7Compound;
Said BaSe is 2.163 grams, said Ga
2Se
3Be 7.526 grams; Be BaSe: Ga
2Se
3=0.01mol: 0.02mol;
The concrete operations step is, in glove box, gets reagent by above-mentioned dose another name, and they are put into mortar, mixes and careful the grinding, in the silica tube of the Φ 12mm * 20mm that packs into then, is evacuated to 10
-3With oxyhydrogen flame the silica tube fusing is encapsulated behind the pa, put into retort furnace, slowly rise to 800 ℃; Its temperature rise rate is 50 ℃/hour, and constant temperature 48 hours takes out after cooling; This moment, sample was more loose, took out sample and ground mixing again, placed silica tube to vacuumize encapsulation again; In 800 ℃ of sintering 24 hours, at this moment sample was shrunk to piece in retort furnace; At this moment, with its taking-up, put into mortar smash to pieces grind Powdered BaGa
4Se
7Compound products.
Adopt Ba+4Ga+7Se=BaGa
4Se
7Reaction formula prepares BaGa with solid reaction process
4Se
7Compound; Said Ba is 1.373 grams, and said Ga is 2.788 grams, and Se is 5.527 gram, i.e. Ba: Ga: Se=0.01mol: 0.04mol: 0.07mol;
Its concrete operations step is, in glove box, gets reagent by above-mentioned dose another name, and they are put into mortar, mixes and careful the grinding, in the silica tube of the Φ 12mm * 20mm that packs into then, is evacuated to 10
-3With flame the silica tube fusing is encapsulated behind the pa, put into retort furnace, slowly rise to 900 ℃; Its temperature rise rate is 10 ℃/hour, and constant temperature 48 hours takes out after cooling; This moment, sample was more loose, took out sample and ground mixing again, placed silica tube to vacuumize encapsulation again; In 900 ℃ of sintering 24 hours, at this moment sample was shrunk to piece in retort furnace; At this moment, with its taking-up, put into mortar smash to pieces grind the preparation Powdered BaGa
4Se
7Compound products.
Adopt BaSe+4Ga+6Se=BaGa
4Se
7Reaction formula prepares BaGa with solid reaction process
4Se
7Compound; Said BaSe is 2.163 grams, and Ga is 2.788 grams, and Se is 4.73 grams; Be BaSe: Ga: Se=0.01mol: 0.04mol: 0.06mol;
The concrete operations step is, the concrete operations step is, in glove box, gets reagent by above-mentioned dose another name, and they are put into mortar, mixes and careful the grinding, in the silica tube of the Φ 12mm * 20mm that packs into then, is evacuated to 10
-3With flame the silica tube fusing is encapsulated behind the pa, put into retort furnace, slowly rise to 950 ℃; Its temperature rise rate is 30 ℃/hour, and constant temperature 48 hours takes out after cooling; This moment, sample was more loose, took out sample and ground mixing again, placed silica tube to vacuumize encapsulation again; In 950 ℃ of sintering 24 hours, at this moment sample was shrunk to piece in retort furnace; At this moment, with its taking-up, put into mortar smash to pieces grind Powdered BaGa
4Se
7Compound products.
Take by weighing 2.163 gram BaSe and 7.526 gram Ga
2Se
3(be BaSe: Ga
2Se
3=0.01mol: 0.02mol), behind the uniform mixing, in the quartz glass tube of the Φ 12mm * 20mm that packs into, be evacuated to 10
-3Behind the handkerchief, be placed in the tubular type reactors with oxyhydrogen flame encapsulation, slowly rise to 1000 ℃, constant temperature 72 hours slowly is cooled to room temperature with the speed of 5 ℃/h, closes the tubular type reactors; Treat silica tube cooling back incision, can obtain the BaGa of yellow transparent
4Se
7Crystal.
Embodiment 5, adopt the KCl flux method to prepare BaGa
4Se
7Crystal.
With gained BaGa among the embodiment 1
4Se
7Powder and KCl fusing assistant are pressed BaGa
4Se
7: KCl=1 weight part: behind the ratio uniform mixing of 2 weight parts, in the quartz glass tube of the Φ 12mm * 20mm that packs into, be evacuated to 10
-3Behind the handkerchief, be placed in the tubular type reactors with the oxyhydrogen flame encapsulation, slowly rise to 850 ℃, constant temperature slowly was cooled to room temperature with 5 ℃/hour speed after 96 hours, closed the tubular type reactors; Treat silica tube cooling back incision, can obtain the BaGa of yellow transparent
4Se
7Crystal.
Embodiment 6, adopt falling crucible method to prepare BaGa
4Se
7Crystal:
Take by weighing 2.163 gram BaSe and 7.526 gram Ga
2Se
3(BaSe: Ga
2Se
3=0.01mol: 0.02mol), behind the uniform mixing, in the quartz glass tube of the Φ 20mm * 30mm that packs into, be evacuated to 10
-3Behind the handkerchief, be placed in the crystal growing furnace, slowly rise to 1050 ℃ and make the raw material fusing with oxyhydrogen flame encapsulation, treat that raw material melts fully after, growing apparatus vertically descends with 0.1-10mm/ hour speed; After crystal growth finished, growing apparatus was reduced to room temperature with 20 hours, obtained the BaGa of yellow transparent
4Se
7Crystal.
Embodiment 7, adopt falling crucible method to prepare BaGa
4Se
7Crystal:
With the BaGa that obtains in embodiment 1,2 or 3
4Se
7Powder is packed in the quartz glass tube of Φ 20mm * 30mm, is evacuated to 10
-3Behind the handkerchief, be placed in the crystal growing furnace with oxyhydrogen flame encapsulation, slowly rise to 1050 ℃ raw material is melted fully after, growing apparatus vertically descends with 0.1-10mm/ hour speed; After crystal growth finished, growing apparatus was reduced to room temperature with 20 hours, obtained the BaGa of yellow transparent
4Se
7Crystal.
Through test, the BaGa that the foregoing description 4-7 is prepared
4Se
7Non-linear optic crystal belongs to oblique system, and spacer is Pc, and its unit cell parameters is:
α=γ=90, β=121.24 (2),
Density: 5.156g/cm
3, have the powder frequency-doubled effect; Fig. 2 is this BaGa
4Se
7The structural representation of non-linear optic crystal.
Embodiment 8:
BaGa with embodiment 4 gained
4Se
7Crystal is done to see through spectrometry, and this crystal is transparent in 0.47 μ m-15 mum wavelength scope; Not easily broken, be easy to cutting, polishing processing and preservation, not deliquescence; BaGa with embodiment 4 gained
4Se
7Crystal is placed on accompanying drawing 1 shown device label and is 3 position, and at room temperature, with transferring Q Nd:YAG laser apparatus to make light source, incident wavelength is the infrared light of 1064nm, and output wavelength is the green laser of 532nm, laser intensity and AgGaS
2Quite.
Accompanying drawing 1 is to adopt BaGa of the present invention
4Se
7The fundamental diagram of a kind of typical nonlinear optics that non-linear optic crystal is processed, wherein 1 is laser apparatus, the 2nd, incoming laser beam, the 3rd, the BaGa after crystal aftertreatment and optics processing
4Se
7Non-linear optic crystal, the 4th, the outgoing laser beam that is produced, the 5th, filter plate; Send incoming laser beam 2 by laser apparatus 1 and inject BaGa
4Se
7Single crystal 3, the outgoing laser beam 4 that is produced passes through filter plate 5, and obtains needed laser beam;
Use BaGa of the present invention
4Se
7The device that non-linear optic crystal is made can be the frequency multiplication producer, upper and lower frequency converter, optical parametric oscillator etc.Laser apparatus 1 can be to mix ream yttrium aluminum garnet (Ho:YAG) laser apparatus or other laser apparatus, does the frequency doubling device of light source using the Ho:YAG laser apparatus, and incoming beam 2 is that wavelength is the infrared light of 2074nm, through BaGa
4Se
7It is 1037 frequency doubled light that non-linear optic crystal produces wavelength, and outgoing beam 4 contains fundamental frequency light that wavelength is 2074nm and the frequency doubled light of 1037nm, 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
4Se
7Compound.
2. said BaGa of claim 1
4Se
7The preparation method of compound, its step is following:
With Ba source material, Ga source material and simple substance Se according to mol ratio Ba: Ga: Se=1: 4: 7 ratio batching and mix after, be heated to 800-950 ℃ and carry out solid state reaction, obtaining chemical formula is BaGa
4Se
7Compound;
Said Ba source material is barium simple substance or barium selenide;
Said Ga source material is gallium simple substance or three selenizings, two galliums.
3. by the said BaGa of claim 2
4Se
7The preparation method of compound is characterized in that, the step that solid state reaction is carried out in said heating is: pack into after above-mentioned batching is ground in the silica tube, silica tube is evacuated to 10
-3Pa also melts encapsulation, puts into retort furnace, is warming up to 800-950 ℃ with 10-50 ℃/hour speed, and constant temperature 48 hours takes out sample after cooling; The sample that takes out is ground mixing again places silica tube to be evacuated to 10 again
-3Pa also melts encapsulation, puts into retort furnace again and is warming up to 800-950 ℃ of sintering 24 hours; Sample is taken out, and smash to pieces grind Powdered BaGa
4Se
7Compound.
4. BaGa
4Se
7Non-linear optic crystal, this BaGa
4Se
7Non-linear optic crystal does not possess has symmetry centre, belongs to oblique system, and spacer is Pc, and its unit cell parameters is:
α=γ=90 °, β=121.24 (2) °.
5. said BaGa of claim 4
4Se
7The preparation method of non-linear optic crystal, it is high-temperature fusant spontaneous crystallization method growth BaGa
4Se
7Non-linear optic crystal the steps include: Powdered BaGa
4Se
7Compound be heated to melt high temperature solution and keep 24-96 hour after, be cooled to room temperature with 1-10 ℃/hour rate of temperature fall, obtain the BaGa of yellow transparent
4Se
7Crystal.
6. by the said BaGa of claim 5
4Se
7The preparation method of non-linear optic crystal is characterized in that, said Powdered BaGa
4Se
7The preparation of compound is following:
With Ba source material, Ga source material and simple substance Se according to mol ratio Ba: Ga: Se=1: 4: 7 mixed evenly after, solid state reaction is carried out in heating, obtaining chemical formula is BaGa
4Se
7Compound, through smash to pieces grind Powdered BaGa
4Se
7Compound;
Said Ba source material is barium simple substance or barium selenide;
Said Ga source material is gallium simple substance or three selenizings, two galliums.
7. said BaGa of claim 4
4Se
7The preparation method of non-linear optic crystal, it is flux method growth BaGa
4Se
7Non-linear optic crystal, its step is following:
With BaGa
4Se
7Compound and fusing assistant are 1 in mass parts: the ratio batching of 0.5-5, be heated to 750-900 ℃ and constant temperature 2-6 days, and reduce to room temperature with 1-10 ℃/hour rate of temperature fall then, obtain the BaGa of yellow transparent
4Se
7Crystal;
Said fusing assistant is KCl, KBr or Li
2Se.
8. said BaGa of claim 4
4Se
7The preparation method of non-linear optic crystal, it is Bridgman-Stockbarge method for growing BaGa
4Se
7Non-linear optic crystal, its step is following:
To contain the Ba raw material, contain the Ga raw material and simple substance Se simple substance is put into crystal growing apparatus, slowly be warming up to the raw material fusing, treat that raw material melts fully after, crystal growing apparatus vertically descends with the speed of 0.1-10mm/h, in crystal growing apparatus decline process, carries out BaGa
4Se
7The non-linear optic crystal growth, its growth cycle is 5-20 days;
Said Ba source material is barium simple substance or barium selenide;
Said Ga source material is gallium simple substance or three selenizings, two galliums.
9. described BaGa of claim 4
4Se
7The purposes of non-linear optic crystal is characterized in that, this BaGa
4Se
7Non-linear optic crystal is used to prepare device for non-linear optical, and prepared device for non-linear optical comprises a branch of at least incidence electromagnetic radiation through at least one this BaGa
4Se
7Produce 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.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2010191140499A CN101767778B (en) | 2010-02-03 | 2010-02-03 | BaGa4Se7Compound and BaGa4Se7Nonlinear optical crystal and its preparation method and use |
Applications Claiming Priority (1)
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