CN102586877B - Raman crystals containing six-membered boron-oxygen rings and growing method and application of the crystals - Google Patents
Raman crystals containing six-membered boron-oxygen rings and growing method and application of the crystals Download PDFInfo
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- CN102586877B CN102586877B CN201210041564.0A CN201210041564A CN102586877B CN 102586877 B CN102586877 B CN 102586877B CN 201210041564 A CN201210041564 A CN 201210041564A CN 102586877 B CN102586877 B CN 102586877B
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Abstract
The invention discloses a kind of Raman crystal and its growing method, purposes comprising boron oxygen hexatomic ring, the chemical formula of the crystalloid is Ba2M (B3O6) 2 (M=Mg, Ca), belongs to trigonal system, R
Space group, this crystalloid can be grown using kyropoulos or czochralski method, and the crystalloid is colorless and transparent, physical and chemical performance is stablized, good mechanical property, easy to cut, polishing, is prepared into quartz crystal device, the ultraviolet absorption edge of the crystalloid is located near 180nm, Raman frequency shift can be used for ultraviolet band, the laser frequency of yellow band and human eye safe waveband near 640cm-1, the laser output of new wave band is obtained, to meet the requirement for crystal Raman frequency conversion diversification.
Description
Technical field
The present invention relates to Raman crystal and growing method, purposes that a class comprises boron oxygen hexatomic ring, belong to artificial crystal growth technical field and laser technology field.
Background technology
Stimulated Raman scattering belongs to third-order nonlinear optical effect, it is a kind of important laser frequency technology, effectively can expand the frequency of existing laser, crystal Raman medium, compared with gas or liquid Raman medium, has the advantages such as particle concentration is large, volume is little, stable performance, pumping threshold is low, heat conductance is good.Compared with the second-order non-linear optical crystal of widespread use, Raman crystal Guang – phototranstormation efficiency is high; With or without symcenter in crystal structure, therefore alternative crystal range is wider; Raman crystal is not strict with optical direction, therefore device design and processing all fairly simple.Along with the development of adjusting the high power laser light such as Q, locked mode technology, the laser technology utilizing Raman crystal to carry out frequency conversion will play an increasingly important role in multiple applications such as laser radar, laser guidance, laser communications, laser medicines.
Raman crystal conventional at present comprises: adamas, BaWO
4, KGd (WO
4)
2, Ba (NO
3)
2, YVO
4, CaCO
3, LiIO
3deng, by the frequency conversion of these crystal can obtain wavelength near 600nm, 1200nm and 1540nm, the Laser output that has significant application value.Such as: the absorption maximum of human body oxyhemoglobin is positioned at 579nm, the laser near this wavelength is highly suitable for neural and blood vessel and carries out operation than the lesions position of comparatively dense.Height 80100 km atmospheric envelopes are irradiated with the gold-tinted laser of 589nm, sodium atom can be caused to resonate, produce back scattering fluorescence, can be used as the artificial with reference to guiding star of ADAPTIVE OPTICS SYSTEMS, significantly increase the sky coverage rate of ADAPTIVE OPTICS SYSTEMS on astronomical telescope.Laser near 1540nm is in the wave band of eye-safe, 400,000 times of 1064nm laser to the exposure of human eye, the laser of this wavelength is also in the 3rd transmission window of air, the low decay corresponding to optical-fibre communications, low dispersion window simultaneously, has good application prospect in fields such as military affairs, optical communications.
Its frequency displacement of Raman crystal conventional is at present generally at 1000cm
-1left and right, ultraviolet absorption edge, near 350nm, still fully can not meet people export diversification requirement to raman laser wavelength, and carry out the requirement of Raman frequency conversion at ultraviolet region.In highly active Raman crystal, usually comprise high symmetrical molecular radical; In these high symmetrical molecular radicals, with the molecular radical with conjugate property, there is better Raman active again.Such as: the Ba (NO comprising high asymmetric conjugate nitrate radical group
3)
2crystal, comprise the CaCO of high asymmetric conjugate carbonate group
3crystal is all the Raman crystal of excellent performance.The structure type of borate crystal is enriched, wherein boron oxygen six-membered ring group (B
3o
6) be the high asymmetric conjugate group of rare similar benzene ring structure in inorganic material.Research has been carried out to multiple physical and chemical performance, growth performance, Raman spectrum and the laser activity comprising the borate crystal of boron oxygen hexatomic ring in recent years in Anhui Inst. of Optics and Fine Mechanics, Chinese Academy of Sciences's crystalline material laboratory.Successively the kind of crystalline of research comprises: α-NaBO
2, α-KBO
2, α-RbBO
2, α-CsBO
2, CsBaB
3o
6, Ba
2mg (B
3o
6)
2, Ba
2ca (B
3o
6)
2and Ba
2sr (B
3o
6)
2totally eight kinds of crystal, find: Ba
2mg (B
3o
6)
2and Ba
2ca (B
3o
6)
2the physical and chemical performance of two kinds of crystal is stable, machining property is good, be easy to preparation, and has that be different from traditional Raman crystal, good Raman spectrum performance and stimulated Raman scattering performance, is the stimulated Raman scattering crystal of a class high comprehensive performance.
Summary of the invention
An object of the present invention is to provide the Raman crystal that a class comprises boron oxygen hexatomic ring, is specifically related to Ba
2mg (B
3o
6)
2and Ba
2ca (B
3o
6)
2two kinds of crystal, to meet the requirement for crystal Raman frequency conversion diversification, another object of the present invention is to provide the growing method of above-mentioned two kinds of crystal.
Object of the present invention can be achieved through the following technical solutions:
One class comprises the Raman crystal of boron oxygen hexatomic ring, it is characterized in that: comprise Ba
2mg (B
3o
6)
2and Ba
2ca (B
3o
6)
2two kinds of crystal, belong to trigonal system, R
space group.
One class comprises the growing method of the Raman crystal of boron oxygen hexatomic ring, it is characterized in that: comprise czochralski method and kyropoulos carries out crystal growth.
One class comprises the growing method of the Raman crystal of boron oxygen hexatomic ring, it is characterized in that comprising the following steps:
(1) the pure BaCO of analysis is stoichiometrically taken
3, CaCO
3, H
3bO
3, first at 350-400 DEG C of sintering 10-13 hour after mixing, after at 750-850 DEG C of sintering 23-25 hour, obtain the Ba of white
2ca (B
3o
6)
2crystal growth raw material;
(2) method of crystal growth by crystal pulling: the crystal growth raw material that step (1) is synthesized is placed in platinum crucible, is warming up to 1100-1250 DEG C, after raw material melts completely, sound out seeded growth temperature, crystal growth is carried out in cooling; Crystal growth parameters is: cooling rate 0.1-0.3 DEG C/h, thermograde 10-50 DEG C/cm near solid-liquid interface, the rotational speed 5-10r/min of crystal, seed crystal direction be a to or c to, pull rate 0.1-1mm/h; Growth cycle 1-2 days; Complete being down to after room temperature through 30h of crystal growth is taken out;
(3) kyropoulos crystal growth: the crystal growth raw material that step (1) is synthesized is placed in platinum crucible, is warming up to 1100-1250 DEG C, after raw material melts completely, sound out seeded growth temperature, crystal growth is carried out in cooling; Crystal growth parameters is: cooling rate 0.02-0.2 DEG C/h, thermograde 5-15 DEG C/cm near solid-liquid interface, the rotational speed 5-10r/min of crystal, seed crystal direction be a to or c to, growth cycle 3-6 days; Crystal growth is complete, is down to after room temperature takes out through 30h.
Comprise the growing method of the Raman crystal of boron oxygen hexatomic ring, it is characterized in that: described CaCO
3(MgCO can be adopted
3)
4mg (OH)
25H
2o replaces, and correspondingly obtains Ba
2mg (B
3o
6)
2crystal growth raw material.
Comprise the purposes of the Raman crystal of boron oxygen hexatomic ring, it is characterized in that: can be used for ultraviolet band, the laser frequency of yellow band and human eye safe waveband; To at least beam of laser, after at least one piece of crystal, produce the new wave band of laser that at least a branch of frequency is different from incident laser frequency, crystal wherein has at least one piece to be Ba
2mg (B
3o
6)
2or Ba
2ca (B
3o
6)
2crystal.
Beneficial effect of the present invention:
Compare traditional Raman crystal, two kinds of crystal provided by the present invention have following advantage: (1) crystal is congruent melting compound, and obtain monocrystalline by czochralski method or kyropoulos, the technical difficulty of crystal growth is little, and the growth cycle of crystal is short; (2) physical and chemical performance of crystal is stablized, and is easy to preserve; Good mechanical property, is easy to processing; The UV-permeable performance that (3) two kinds of crystal have had, can be used for the Raman frequency conversion of ultraviolet band; (4) above-mentioned two kinds of crystal have unique Raman frequency shift wave number, by using together with other frequency-changer crystals, can obtain the laser of multiple new wave band.
Accompanying drawing explanation
Fig. 1 is Ba prepared by embodiment 2
2mg (B
3o
6)
2crystal, bottom right illustration is the Ba through oriented machining
2mg (B
3o
6)
2wafer.
Fig. 2 is Ba
2mg (B
3o
6)
2crystal transmittance curve.
Fig. 3 is Ba
2mg (B
3o
6)
2crystal and Ba
2ca (B
3o
6)
2the Raman spectrum of crystal.Wherein: 1:Ba
2ca (B
3o
6)
2the Raman spectrum of crystal; 2:Ba
2mg (B
3o
6)
2the Raman spectrum of crystal.
Fig. 4 is typical Ba
2m (B
3o
6)
2(M=Mg, Ca) crystal carries out the schematic diagram of Raman frequency conversion.Wherein, 3: high power incident laser; 4: input mirror; 5: outgoing mirror; 6:Ba
2m (B
3o
6)
2(M=Mg, Ca) crystal; 7: the raman laser obtained through frequency conversion.
Embodiment
In order to better understand the present invention, below in conjunction with embodiment, the present invention will be further described, but the scope of protection of present invention is not limited to the scope that embodiment represents.
embodiment 1: kyropoulos growth Ba
2
mg (B
3
o
6
)
2
crystal
Stoichiometrically take analytically pure BaCO
3, (MgCO
3)
4mg (OH)
25H
2o and H
3bO
3, they are fully ground, mix after insert in corundum crucible, put into muffle furnace, be warming up to 400
oc is also down to room temperature after being incubated 12 hours.Again grind sintering the intermediate product obtained for the first time, mix and insert in corundum crucible, put into muffle furnace, be warming up to 780
oc is also incubated 24 hours, takes out, obtain Ba after naturally cooling to room temperature
2mg (B
3o
6)
2crystal growth raw material.Its reaction equation is:
2H
3BO
3=B
2O
3+3H
2O↑
10BaCO
3+(MgCO
3)
4·Mg(OH)
2·5H
2O+15B
2O
3= 5Ba
2Mg(B
3O
6)
2+14CO
2↑+6H
2O↑
The polycrystalline growth raw material obtained is inserted in the platinum crucible being of a size of Φ 50mm × 40mm, puts into the raw stove of bubble, be warming up to 1100
oc, after growth raw material melts completely, constant temperature 4 ~ 8 hours, is adjusted to crystal growth temperature, under enter seed crystal and carry out crystal growth.Crystal growth parameters is: rate of temperature fall is 1.0
oc/ days, the rotating speed 10r/min of crystal, the thermograde 10 near solid-liquid interface
oc/cm, seed crystal direction be c to.Crystal growth stopped growing after 4 days, after 30 hours, be down to room temperature, obtained being of a size of the completely transparent Ba of Φ 30mm × 5mm
2mg (B
3o
6)
2crystal, as shown in Figure 1.
This crystal is placed 5 months in atmospheric environment, keeps transparent.Irradiate crystal with the laser of 532nm wavelength and can produce yellowish green laser.
embodiment 2: Czochralski grown Ba
2
ca (B
3
o
6
)
2
crystal
Stoichiometrically take analytically pure BaCO
3, CaCO
3and H
3bO
3, the potpourri taken is placed in corundum crucible through grinding, mixing, is warming up to 400
oc, is down to room temperature after constant temperature 12h.The raw material sintered for the first time is ground again, mix after insert in corundum crucible, be warming up to 800
oc, is down to room temperature after constant temperature 24h, obtains the Ba of white
2ca (B
3o
6)
2crystal growth raw material.Chemical equation is as follows:
2H
3BO
3= B
2O
3+3H
2O↑
2BaCO
3+CaCO
3+3B
2O
3= Ba
2Ca(B
3O
6)
2+3CO
2↑
The crystal growth raw material obtained is inserted in the platinum crucible being of a size of Φ 50mm × 40mm, is warming up to 1180
oc, after growth raw material melts completely, constant temperature 4 ~ 8 hours, is adjusted to crystal growth temperature, under enter seed crystal and carry out crystal growth.Crystal growth parameters is: rate of temperature fall is 4
oc/ days, the rotating speed 10r/min of crystal, the thermograde 30 near solid-liquid interface
oc/cm, the direction of growth along crystallographic axis a direction, pull rate 0.3mm/h.Stop growing after 36 hours, be down to room temperature through 30 hours, take out crystal, obtain the monocrystalline of the partially transparent being of a size of 30mm × 40mm × 13mm.
This crystal is placed 5 months in atmospheric environment, keeps transparent.Irradiate crystal with the laser of 532nm wavelength and can produce yellowish green laser.
embodiment 3:Ba
2
mg (B
3
o
6
)
2
crystal transmittance
By the Ba obtained in embodiment 1
2mg (B
3o
6)
2monocrystalline is processed into 5 × 5 × 1mm thin slice, and adopt VARIAN CARY-5E spectrophotometer measurement its ultraviolet-visible-near infrared transmittance spectrum, measurement range is 175-3300nm.As shown in Figure 2, result shows its transmittance curve: the ultraviolet cut-on limit of this crystal reaches 178nm, in its transmitance of 3300nm place still close to 80%.
embodiment 4:Ba
2
mg (B
3
o
6
)
2
and Ba
2
ca (B
3
o
6
)
2
crystal Raman spectrum
By the Ba obtained in embodiment 1 and 2
2mg (B
3o
6)
2and Ba
2ca (B
3o
6)
2crystal carries out Raman spectrum test.Experiment adopts Jobin Y ' von Raman spectrometer, excitation source is Q impulse THG-Nd:YAG laser instrument, excitation wavelength is 355nm, output power is 0.8w, light path adopts the confocal collection system of backward scattering, scattered light focuses on the entrance slit of monochromator, and slit width is 300 μm, and spectral resolution is about 2cm
-1.As shown in Figure 3, result shows its Raman spectrum: Ba
2mg (B
3o
6)
2the Raman vibration peak that breathing vibration pattern is corresponding the strongest, its Raman frequency shift is positioned at: 645cm
-1, halfwidth is: 13cm
-1; Ba
2ca (B
3o
6)
2the Raman vibration peak that breathing vibration pattern is corresponding the strongest, its Raman frequency shift is positioned at 639cm
-1, halfwidth is: 10cm
-1.
embodiment 5: applicating example 1
The wavelength produced by Nd:YAG is the infrared laser of 1064nm, after electric-optically Q-switched, then through Ba
2mg (B
3o
6)
2raman crystal frequency conversion realizes 1142nm Laser output, and its schematic diagram as shown in Figure 4.
embodiment 6: applicating example 2
By the frequency doubled light of Nd:YAG laser, wavelength is the laser of 532nm, again through Ba after electric-optically Q-switched
2ca (B
3o
6)
2raman crystal frequency conversion realizes 550nm gold-tinted Laser output, and its schematic diagram as shown in Figure 4.
Claims (2)
1. a class comprises the growing method of the Raman crystal of boron oxygen hexatomic ring, it is characterized in that: comprise Ba
2mg (B
3o
6)
2and Ba
2ca (B
3o
6)
2the growing method of two kinds of crystal, belongs to trigonal system,
space group; Kyropoulos is adopted to carry out crystal growth;
Ba
2mg (B
3o
6)
2the kyropoulos growing method of crystal:
(1) the pure BaCO of analysis is stoichiometrically taken
3, (MgCO
3)
4mg (OH)
25H
2o, H
3bO
3, first at 350-400 after mixing
oc sinters 10-13 hour, after at 750-850
oc sinters 23-25 hour, obtains the Ba of white
2mg (B
3o
6)
2crystal growth raw material;
(2) the crystal growth raw material that step (1) is synthesized is placed in platinum crucible, is warming up to 1100-1250
oc, after raw material melts completely, sound out seeded growth temperature, crystal growth is carried out in cooling; Crystal growth parameters is: cooling rate 0.02-0.2
oc/h, the thermograde 5-15 near solid-liquid interface
oc/cm, the rotational speed 5-10r/min of crystal, seed crystal direction is
axiang Huo
cto, growth cycle 3-6 days; Crystal growth is complete, is down to after room temperature takes out through 30h;
Ba
2ca (B
3o
6)
2the kyropoulos growing method of crystal:
(1) the pure BaCO of analysis is stoichiometrically taken
3, CaCO
3, H
3bO
3, first at 350-400 DEG C of sintering 10-13 hour after mixing, after at 750-850 DEG C of sintering 23-25 hour, obtain the Ba of white
2ca (B
3o
6)
2crystal growth raw material;
(2) the crystal growth raw material that step (1) is synthesized is placed in platinum crucible, is warming up to 1100-1250 DEG C, after raw material melts completely, sound out seeded growth temperature, crystal growth is carried out in cooling; Crystal growth parameters is: cooling rate 0.02-0.2 DEG C/h, thermograde 5-15 DEG C/cm near solid-liquid interface, the rotational speed 5-10r/min of crystal, seed crystal direction be a to or c to, growth cycle 3-6 days; Crystal growth is complete, is down to after room temperature takes out through 30h.
2. a purposes for what growing method as claimed in claim 1 obtained the comprise Raman crystal of boron oxygen hexatomic ring, is characterized in that: can be used for ultraviolet band, the laser frequency of yellow band and human eye safe waveband; To at least beam of laser, after at least one piece of crystal, produce the new wave band of laser that at least a branch of frequency is different from incident laser frequency, crystal wherein has at least one piece to be Ba
2mg (B
3o
6)
2or Ba
2ca (B
3o
6)
2crystal.
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| CN102677171B (en) * | 2012-05-03 | 2015-04-15 | 中国科学院理化技术研究所 | Barium boric acid calcium birefringent crystal, growth method and application |
| CN104746141A (en) * | 2015-03-30 | 2015-07-01 | 山东省科学院新材料研究所 | Raman crystal as well as growth method and application thereof |
| CN105063753A (en) * | 2015-08-28 | 2015-11-18 | 中国科学院上海硅酸盐研究所 | Czochralski method growth process of sodium nitrate monocrystalline |
| CN107604438A (en) * | 2017-09-28 | 2018-01-19 | 中国科学院理化技术研究所 | Purposes of the Firebrake ZB crystal in Raman crystal |
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| CN102839421A (en) * | 2011-06-21 | 2012-12-26 | 中国科学院理化技术研究所 | Borate birefringent crystal for ultraviolet and deep ultraviolet, and growth method and application thereof |
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| CN102839421A (en) * | 2011-06-21 | 2012-12-26 | 中国科学院理化技术研究所 | Borate birefringent crystal for ultraviolet and deep ultraviolet, and growth method and application thereof |
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