CN101767778A - BaCa4Se7 compound, BaCa4Se7 nonlinear optical crystal, preparation method and application - Google Patents

BaCa4Se7 compound, BaCa4Se7 nonlinear optical crystal, preparation method and application Download PDF

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CN101767778A
CN101767778A CN201019114049A CN201019114049A CN101767778A CN 101767778 A CN101767778 A CN 101767778A CN 201019114049 A CN201019114049 A CN 201019114049A CN 201019114049 A CN201019114049 A CN 201019114049A CN 101767778 A CN101767778 A CN 101767778A
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baga
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CN101767778B (en
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姚吉勇
梅大江
傅佩珍
吴以成
陈创天
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Technical Institute of Physics and Chemistry of CAS
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Abstract

The invention relates to a BaCa4Se7 compound, a BaCa4Se7 nonlinear optical crystal, a preparation method and application. The BaCa4Se7 compound is prepared by adopting a solid-phase reaction, and the BaCa4Se7 nonlinear optical crystal is grown by adopting a high-temperature melt spontaneous crystallization method, a flux growth method or a Bridgman method. In the growth of the BaCa4Se7 nonlinear optical crystal, the crystal is easy to grow and transparent and has no package and the advantages of higher growing speed, low cost, easy obtaining of a crystal in a larger size, and the like. The obtained BaCa4Se7 nonlinear optical crystal has the advantages of wider optical transparency range, larger hardness, good mechanical property, difficult cracking and deliquescence, easy processing and storage, and the like. The BaCa4Se7 nonlinear optical crystal can be used for preparing a nonlinear optical device.

Description

BaGa 4Se 7Compound, BaGa 4Se 7Non-linear optic crystal and method for making and purposes
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 make second harmonic generator, upper and lower frequency converter, device for non-linear optical such as optical parametric oscillator.The laser that laser apparatus produces can carry out frequency inverted by device for non-linear optical, thereby obtains the laser of how useful wavelength, and laser apparatus is more widely used.According to the difference of material application band, can be divided into ultraviolet region, visible and near-infrared region and mid-infrared light district nonlinear optical material three major types.The non-linear optical crystal material of visible region and ultraviolet region can satisfy requirement of actual application; As the practical KTP (KTiOPO that mainly contains in two frequencys multiplication (532nm) crystal 4), BBO (β-BaB 2O 4), LBO (LiB 3O 5) crystal; Practical in frequency tripling (355nm) crystal have BBO, LBO, a CBO (CsB 3O 5) available.And the development of the nonlinear crystal of infrared band is slow; The material in infrared light district is ABC mostly 2The chalcopyrite structure semiconductor material of type is as AgGaQ 2(Te), the too low and crystal growth difficulty of the light injury threshold of infrared non-linear crystal has directly influenced actual use for Q=S, Se.The middle-infrared band non-linear optic crystal has important use at optoelectronic areas, and for example it can extend to middle infrared with the laser (as 1.064 μ m) of near-infrared band by means such as optical parametric oscillation or optical parameter amplifications; Also can be to the important laser in mid-infrared light district (as CO 2Laser, 10.6 μ m) carry out frequency multiplication, this is significant for obtaining the continuously adjustable laser of wavelength.Therefore the novel infrared nonlinear optical crystal material of seeking premium properties has become one of the difficult point of current nonlinear optical material research field and forward position direction.
Summary of the invention
It is 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 as follows:
The invention provides a kind of chemical formula is BaGa 4Se 7Compound.
BaGa provided by the invention 4Se 7The preparation method of compound, its step is as follows:
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;
Described Ba source material is barium simple substance or barium selenide;
Described Ga source material is for sowing simple substance or three selenizings two are sowed.
The step that solid state reaction is carried out in described heating is: pack into after above-mentioned batching is ground in the silica tube, silica tube is evacuated to 10 -3Pa also melts encapsulation, puts into retort furnace, is warming up to 800-950 ℃ 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.
Described BaGa 4Se 7Compound can prepare by following chemical equation:
(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 symmetry centre, belongs to oblique system, and spacer is Pc, and its unit cell parameters is: a=7.6252 (15)
Figure GSA00000019388600021
, b=6.5114 (13)
Figure GSA00000019388600022
, c=14.7020 (40)
Figure GSA00000019388600023
, 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.
Described Powdered BaGa 4Se 7Being prepared as follows of compound:
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;
Described Ba source material is barium simple substance or barium selenide;
Described Ga source material is for sowing simple substance or three selenizings two are sowed.
Described BaGa 4Se 7Compound can prepare by following chemical equation:
(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 as follows:
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;
Described 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 as follows:
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, carries out BaGa in crystal growing apparatus decline process 4Se 7The non-linear optic crystal growth, its growth cycle is 5-20 days;
Described Ba source material is barium simple substance or barium selenide;
Described 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 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 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,,,, promptly can be used as device for non-linear optical and use this BaGa the logical light mirror polish of crystal by required angle, thickness and sectional dimension sliced crystal with crystal blank orientation 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 by 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, the non-linear optic crystal of this compound and its production and use have following effect:
At this BaGa 4Se 7The growing crystals of non-linear optic crystal is easily grown up and transparent nothing parcel, and it is very fast to have the speed of growth, and cost is low, obtains advantages such as large-size crystal easily; The 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 made, 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
EXAMPLE l prepares Powdered BaGa 4Se 7Compound:
Adopt BaSe+2Ga 2Se 3=BaGa 4The Se reaction formula prepares BaGa with solid reaction process 4Se 7Compound;
Described BaSe is 2.163 grams, described Ga 2Se 3Be 7.526 grams; Be BaSe: Ga 2Se 3=0.01mol: 0.02mol;
The concrete operations step is, takes by weighing reagent respectively by above-mentioned dosage in glove box, and they are put into mortar, mixes and careful the grinding, in the silica tube of the Φ 12mm * 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, constant temperature 48 hours, take 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.
Embodiment 2, prepare Powdered BaGa 4Se 7Compound:
Adopt Ba+4Ga+7Se=BaGa 4Se 7Reaction formula prepares BaGa with solid reaction process 4Se 7Compound; Described Ba is 1.373 grams, and described 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, take by weighing reagent respectively by above-mentioned dosage, they are put into mortar, mix and careful the grinding, pack into then in the silica tube of Φ 12mm * 20mm, with flame the silica tube fusing is encapsulated after being evacuated to 10-3pa, put into retort furnace, slowly rise to 900 ℃, its temperature rise rate is 10 ℃/hour, constant temperature 48 hours takes out after cooling, and this moment, sample was more loose, take out sample and grind mixing again, place 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.
Embodiment 3, prepare Powdered BaGa 4Se 7Compound.
Adopt BaSe+4Ga+6Se=BaGa 4Se 7Reaction formula prepares BaGa with solid reaction process 4Se 7Compound; Described 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, takes by weighing reagent respectively by above-mentioned dosage in glove box, and they are put into mortar, mixes and careful the grinding, in the silica tube of the Φ 12mm * 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, constant temperature 48 hours, take 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.
Embodiment 4, adopt high-temperature fusant spontaneous crystallization legal system to be equipped with BaGa 4Se 7Crystal:
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 growth furnace 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 growth furnace; 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 growth furnace 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 growth furnace; 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.
After tested, the prepared BaGa of the foregoing description 4-7 4Se 7Non-linear optic crystal belongs to oblique system, and spacer is Pc, and its unit cell parameters is: a=7.6252 (15) , b=6.5114 (13)
Figure GSA00000019388600062
, c=14.702 (4) α=γ=90, β=121.24 (2), Z=2, V=624.1
Figure GSA00000019388600064
3, 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 made, 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 No:YAG laser apparatus, and incoming beam 2 is that wavelength is the infrared light of 2074nm, passes 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 (10)

1. a chemical formula is BaGa 4Se 7Compound.
2. described BaGa of claim 1 4Se 7The preparation method of compound, its step is as follows:
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;
Described Ba source material is barium simple substance or barium selenide;
Described Ga source material is for sowing simple substance or three selenizings two are sowed.
3. by the described BaGa of claim 2 4Se 7The preparation method of compound is characterized in that, the step that solid state reaction is carried out in described heating is: pack into after above-mentioned batching is ground in the silica tube, silica tube is evacuated to 10 -3Pa also melts encapsulation, puts into retort furnace, is warming up to 800-950 ℃ 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 symmetry centre, belongs to oblique system, and spacer is Pc, and its unit cell parameters is: a=7.6252 (15)
Figure FSA00000019388500011
, b=6.5114 (13)
Figure FSA00000019388500012
C=14.7020 (40)
Figure FSA00000019388500013
, α=γ=90 °, β=121.24 (2) °.
5. described 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 described BaGa of claim 4 4Se 7The preparation method of non-linear optic crystal is characterized in that, described Powdered BaGa 4Se 7Being prepared as follows of compound:
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;
Described Ba source material is barium simple substance or barium selenide;
Described Ga source material is for sowing simple substance or three selenizings two are sowed.
7. described 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 as follows:
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;
Described fusing assistant is KCl, KBr or Li 2Se.
8. described 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 as follows:
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, carries out BaGa in crystal growing apparatus decline process 4Se 7The non-linear optic crystal growth, its growth cycle is 5-20 days;
Described Ba source material is barium simple substance or barium selenide;
Described Ga source material is for sowing simple substance or three selenizings two are sowed.
9. by the described BaGa of claim 8 4Se 7The preparation method of non-linear optic crystal is characterized in that, also comprises BaGa 4Se 7The 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.
10. 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 by 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.
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