CN106283193A - Bromine gallium barium borate sodium and bromine gallium barium borate sodium nonlinear optical crystal and preparation method and purposes - Google Patents
Bromine gallium barium borate sodium and bromine gallium barium borate sodium nonlinear optical crystal and preparation method and purposes Download PDFInfo
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Abstract
The present invention relates to a kind of bromine gallium barium borate sodium and bromine gallium barium borate sodium nonlinear optical crystal and preparation method and purposes, the chemical formula of this compound is NaBa4Ga2B8O18Br3, molecular weight 1326.00, use solid reaction process to prepare, bromine gallium barium borate sodium nonlinear optical crystal, chemical formula is NaBa4Ga2B8O18Br3, molecular weight 1326.00, not there is symmetrical centre, belong to tetragonal crystal system, space group P4 (2) nm, cell parameter is a=12.347 (17), b=12.347 (17), c=6.911 (19), V=1053 (3)3, its powder SHG effect reaches KDP (KH2PO4) 2.1 times, ultraviolet cut-on limit is about 334nm；Use high temperature solution method growth crystal, the bromine gallium barium borate sodium nonlinear optical crystal mechanical hardness obtained by the method for the invention is big, it is prone to cutting, polishing and preservation, is used widely in the device for non-linear optical such as preparation times frequency generator, upper frequency transducer, lower frequency transducer or optical parametric oscillator.
Description
Technical field
The present invention relates to a kind of compound bromine gallium barium borate sodium and bromine gallium barium borate sodium nonlinear optical crystal and preparation method and
Purposes, chemical formula is NaBa4Ga2B8O18Br3。
Background technology
Utilize the nonlinear optical effect of crystal, second harmonic generator, upper and lower frequency converter, optical parameter can be made
The device for non-linear optical such as agitator.The laser that laser instrument produces can carry out frequency conversion by device for non-linear optical, thus
Obtain the laser of more useful wavelength, make laser instrument be more widely used.In non-linear optical crystal material, Halogen
The nonlinear optical crystal of element is the crystalline material that a class is unique.Because halide ion has the biggest on coordination structure
Similarity, their physicochemical properties make halide ion when mutually replacing (partly or entirely), are not result in crystal
The sudden change of structure, thus easily realize the modification of material.
Explore frequency-doubled effect big, through wide waveband, light injury threshold is big, physical and chemical performance is stable novel non-linearity optics simultaneously
Crystal, the always much-talked-about topic in laser frequency field.Currently mainly nonlinear optical material has: BBO (β-BaB2O4)、
LBO(LiB3O5) crystal, CBO (CsB3O5) crystal, CLBO (CsLiB6O10) crystal and KBBF (KBe2BO3F2) crystal.
Although the crystal technique of these materials reaches its maturity, but there are still clearly disadvantageous part: deliquescence as easy in crystal,
Growth cycle length, layer growth habit are serious and expensive.Therefore, new non-linear optical crystal material is found still
It is that one extremely important and large order.
For making up the deficiency of above nonlinear optical crystal, various countries scientist is still in doing one's utmost to pay close attention to all kinds of novel non-linearity light
Learn exploration and the research of crystal, not only focus on optical property and the mechanical performance of crystal, and increasingly pay attention to the preparation of crystal
Characteristic.Find the nonlinear optical crystal of practicality, by nonlinear optical effects such as frequency multiplication, mixing, optical parametric oscillations, can
Limited optical maser wavelength is converted into the laser of new wave band.Utilize this technology can fill up all kinds of Laser Devices and launch laser wave
Long blank spectral regions, make laser instrument be more widely used.
Summary of the invention
Present invention aim at providing a kind of compound bromine gallium barium borate sodium, the chemical formula of this compound is
NaBa4Ga2B8O18Br3, molecular weight 1326.00, use solid reaction process to prepare bromine gallium barium borate sodium compound.
Another object of the present invention is to provide a kind of bromine gallium barium borate sodium nonlinear optical crystal, and the chemical formula of this crystal is
NaBa4Ga2B8O18Br3, not there is symmetrical centre, belong to tetragonal crystal system, space group P4 (2) nm, cell parameter is
Still a further object of the present invention is to provide the preparation method of a kind of bromine gallium barium borate sodium device for non-linear optical.
Another object of the present invention is to provide the purposes of a kind of bromine gallium barium borate sodium device for non-linear optical, and is used as preparation times
Frequency generator, upper frequency transducer, lower frequency transducer or optical parametric oscillator.
A kind of compound bromine gallium barium borate sodium of the present invention, the chemical formula of this compound is NaBa4Ga2B8O18Br3, molecule
Amount 1326.00, uses solid reaction process to prepare bromine gallium barium borate sodium compound.
A kind of bromine gallium barium borate sodium nonlinear optical crystal, the chemical formula of this crystal is NaBa4Ga2B8O18Br3, molecular weight
1326.00, not there is symmetrical centre, belong to tetragonal crystal system, space group P4 (2) nm, cell parameter is
The preparation method of described bromine gallium barium borate sodium nonlinear optical crystal, uses high temperature solution method growth crystal, specifically grasps
Make to follow these steps to carry out:
A, it is brium carbonate, barium nitrate, Barium monoxide, barium hydroxide, barium bicarbonate or barium oxalate by containing barium compound；Barium bromide,
Sodium bromide, gallium oxide and boric acid or boron oxide are during 7:2:1:2:16-8 puts into mortar in molar ratio, and mixing is also carefully ground, so
In the opening corundum crucible of rear loading Φ 100mm × 100mm, put in Muffle furnace, be to slowly warm up to 550 DEG C, constant temperature 24
Hour, take out crucible after cooling, now sample is more loose, takes out sample and re-grinds uniformly, then is placed in crucible,
In temperature 800 DEG C constant temperature 48 hours again in Muffle furnace, it is drawn off, puts into mortar is smashed to pieces and grind and get final product
NaBa4Ga2B8O18Br3Compound, carries out X-ray analysis, gained X-ray spectrogram and bromine gallium barium borate sodium to this product
NaBa4Ga2B8O18Br3The X-ray spectrogram that mono-crystalline structures obtains is consistent；
B, bromine gallium barium borate sodium compound single-phase polycrystalline powder step a obtained and flux are LiBr, LiBr-H3BO3、
LiBr-PbO、H3BO3-PbO, LiBr-PbO or KBr-PbO 1:3-10 in molar ratio uniformly mixes, and loads Φ 80mm × 80mm
Opening platinum crucible in, be heated to temperature 820-1050 DEG C with the heating rate of temperature 1-30 DEG C/h, constant temperature 5-80 hour,
Obtain mixed molten liquid, then be cooled to 685-760 DEG C；
Or directly 7:2:1:2:16:3-10 weighs containing barium compound in molar ratio is brium carbonate, barium nitrate, Barium monoxide, hydrogen-oxygen
Change barium, barium bicarbonate or barium oxalate；Barium bromide, sodium bromide, gallium oxide and boric acid or boron oxide and flux be LiBr,
LiBr-H3BO3、LiBr-PbO、H3BO3-PbO, LiBr-PbO or KBr-PbO uniformly mix, and load Φ 80mm × 80mm's
In opening platinum crucible, it is heated to temperature 820-1050 DEG C with the heating rate of temperature 1-30 DEG C/h, constant temperature 5-80 hour,
Obtain mixed molten liquid, then be cooled to 685-760 DEG C；
C, prepare bromine gallium barium borate sodium seed crystal: mixed molten liquid step b obtained is slow with the speed of temperature 0.5-10 DEG C/h
Being down to room temperature, spontaneous crystallization obtains bromine gallium barium borate sodium seed crystal；
D, inserting in crystal growing furnace by filling the crucible of mixed molten liquid that step b prepares, seed crystal step c obtained is fixed
On seed rod, seed crystal from crystal growing furnace top, first preheating seed crystal 5-60 minute, by seed crystal down to contact mixed molten liquid
Liquid level or immersion mixed molten liquid carry out melt back, constant temperature 5-60 minute, is cooled to the speed of temperature 1-60 DEG C/h
780-855℃；
E, again with temperature 0.1-5 DEG C/day speed slow cooling, carry out the life of crystal with 0-60rpm rotating speed rotary seed crystal rod
Long, after required yardstick is arrived in crystal growth, by crystal lift-off mixed molten liquid surface, and it is down to room with temperature 1-80 DEG C/h speed
Temperature, then takes out crystal from burner hearth, i.e. prepares bromine gallium barium borate sodium nonlinear optical crystal.
LiBr-H in step b3BO3LiBr and H in flux3BO3Mol ratio be 1-8:1-5；H3BO3In-PbO flux
H3BO3It is 1-6:1-5 with the mol ratio of PbO；Bromide in LiBr-PbO, LiBr-PbO or KBr-PbO flux and oxygen
The mol ratio changing lead is 2-5:1-3.
Described bromine gallium barium borate sodium nonlinear optical crystal is in preparation times frequency generator, upper frequency transducer, lower frequency conversion
Purposes in device or optical parametric oscillator.
Compound bromine gallium barium borate sodium of the present invention, its chemical formula is NaBa4Ga2B8O18Br3, molecular weight 1326.00,
Solid reaction process is used to prepare bromine gallium barium borate sodium compound by following chemical equation:
(1)7BaCO3+2NaBr+BaBr2+2Ga2O3+16H3BO3→2NaBa4Ga2B8O18Br3+7CO2↑+24H2O↑；
(2)7Ba(NO3)2+2NaBr+BaBr2+2Ga2O3+16H3BO3→2NaBa4Ga2B8O18Br3+13NO2↑+NO↑+24H2O↑+4O2↑；
(3)7BaO+2NaBr+BaBr2+2Ga2O3+16H3BO3→2NaBa4Ga2B8O18Br3+24H2O↑；
(4)7Ba(OH)2+2NaBr+BaBr2+2Ga2O3+16H3BO3→2NaBa4Ga2B8O18Br3+31H2O↑；
(5)7Ba(HCO3)2+2NaBr+BaBr2+2Ga2O3+16H3BO3→2NaBa4Ga2B8O18Br3+14CO2↑+31H2O↑；
(6)7BaCO3+2NaBr+BaBr2+2Ga2O3+8B2O3→2NaBa4Ga2B8O18Br3+7CO2↑；
(7)7Ba(NO3)2+2NaBr+BaBr2+2Ga2O3+8B2O3→2NaBa4Ga2B8O18Br3+13NO2↑+NO↑+4O2↑；
(8)7BaO+2NaBr+BaBr2+2Ga2O3+8B2O3→2NaBa4Ga2B8O18Br3；
(9)7Ba(OH)2+2NaBr+BaBr2+2Ga2O3+8B2O3→2NaBa4Ga2B8O18Br3+7H2O↑；
(10)7Ba(HCO3)2+2NaBr+BaBr2+2Ga2O3+8B2O3→2NaBa4Ga2B8O18Br3+14CO2↑+7H2O↑；
(11)7BaC2O4+2NaBr+BaBr2+2Ga2O3+8B2O3→2NaBa4Ga2B8O18Br3+7CO2↑+7CO↑。
Bromine gallium barium borate sodium nonlinear optical crystal of the present invention, its chemical formula is NaBa4Ga2B8O18Br3, molecular weight
1326.00, not there is symmetrical centre, belong to tetragonal crystal system, space group P4 (2) nm, cell parameter is Its powder SHG effect reaches KDP (KH2PO4)
2.1 times, ultraviolet cut-on limit is about 334nm.
Owing to, during growth bromine gallium barium borate sodium nonlinear optical crystal, employing LiBr, LiBr-H3BO3、LiBr-PbO、
LiBr-PbO、H3BO3-PbO or KBr-PbO flux, product purity is high, and crystal is easily grown up and transparent without parcel, has life
Long speed, low cost, it is readily available the advantages such as large-size crystal；Obtained crystal has relatively wide transmission region,
Hardness is relatively big, good mechanical property, not easily broken and deliquescence, it is easy to process and the advantage such as preservation；Use the bromine gallium boron of the present invention
The device for non-linear optical that acid barium sodium nonlinear optical crystal is made, at room temperature, makees light source with Nd:YAG Q-switched laser,
Incident wavelength is the infrared light of 1064nm, and output wavelength is the green laser of 532nm, and laser intensity is equivalent to KDP (KH2PO4)
2.1 times.
Accompanying drawing explanation
Fig. 1 is the NaBa of the present invention4Ga2B8O18Br3The X-ray diffraction figure of powder；
Fig. 2 is the crystal pattern of the present invention；
Fig. 3 is the fundamental diagram of the device for non-linear optical of the present invention, and wherein 1 is laser instrument, and 2 for sending light beam, 3
For NaBa4Ga2B8O18Br3Crystal, 4 is outgoing beam, and 5 is filter plate.
Detailed description of the invention
Below in conjunction with drawings and Examples, the present invention is described in detail:
Embodiment 1:
By reaction equation: 7BaCO3+2NaBr+BaBr2+2Ga2O3+16H3BO3→2NaBa4Ga2B8O18Br3+7CO2↑+24H2O ↑ synthesis
NaBa4Ga2B8O18Br3Compound:
By BaCO3、NaBr、BaBr2、Ga2O3、H3BO3During 7:2:1:2:16 puts into mortar in molar ratio, mixing is also carefully ground
Mill, is then charged in the opening corundum crucible of Φ 100mm × 100mm, puts in Muffle furnace, be to slowly warm up to 550 DEG C, permanent
Temperature 24 hours, takes out crucible after cooling, and now sample is more loose, takes out sample and re-grinds uniformly, then is placed in crucible,
In temperature 800 DEG C constant temperature 48 hours again in Muffle furnace, it is drawn off, puts into mortar to be smashed to pieces grind and i.e. obtain compound
NaBa4Ga2B8O18Br3, this product is carried out X-ray analysis, gained X-ray spectrogram and bromine gallium barium borate sodium NaBa4Ga2B8O18Br3
The X-ray spectrogram that mono-crystalline structures obtains is consistent；
The compound bromine gallium barium borate sodium NaBa that will obtain4Ga2B8O18Br3Single-phase polycrystalline powder is with flux LiBr in molar ratio
NaBa4Ga2B8O18Br3: LiBr=1:3 carries out mixture, loads in the opening platinum crucible of Φ 80mm × 80mm, with 30 DEG C/h of temperature
Heating rate be heated to 880 DEG C, constant temperature 15 hours, obtain mixed molten liquid, then be cooled to 685 DEG C；
Prepare bromine gallium barium borate sodium seed crystal: obtain bromine with the speed slow cooling of 0.5 DEG C/h of temperature to room temperature, spontaneous crystallization
Gallium barium borate sodium seed crystal；
The crucible filling prepared mixed molten liquid is inserted in crystal growing furnace, the seed crystal obtained is fixed on seed rod, from crystalline substance
Bulk-growth furnace roof subordinate's seed crystal, first preheating seed crystal 5 minutes, immerses seed crystal and carries out melt back in mixed molten liquid, constant temperature 5 minutes,
It is cooled to 855 DEG C with the speed of 15 DEG C/h of temperature；
Lower the temperature with the speed of temperature 0.1 DEG C/day again, with the rotating speed rotary seed crystal rod of 10rpm, after crystal growth terminates, make
Crystal departs from liquid level, is down to room temperature with the speed of temperature 1 DEG C/h, can obtain a size of 56mm × 40mm × 30mm's
NaBa4Ga2B8O18Br3Nonlinear optical crystal.
Oxide spinel barium in reaction equation can be replaced by Barium monoxide or barium nitrate or barium oxalate or barium hydroxide or barium bicarbonate,
Boric acid can be replaced by boron oxide.
Embodiment 2:
By reaction equation: 7Ba (NO3)2+2NaBr+BaBr2+2Ga2O3+16H3BO3→2NaBa4Ga2B8O18Br3+13NO2↑
+NO↑+24H2O↑+4O2↑ synthesis NaBa4Ga2B8O18Br3Compound:
By Ba (NO3)2、NaBr、BaBr2、Ga2O3、H3BO37:2:1:2:16 directly weighs raw material in molar ratio, by weigh
Raw material and flux KBr-PbO 1:4 in molar ratio carry out mixture, and wherein the mol ratio of KBr Yu PbO is 2:1, load
In the opening platinum crucible of Φ 80mm × 80mm, it is warming up to 820 DEG C with the heating rate of 1 DEG C/h of temperature, constant temperature 5 hours,
Obtain mixed molten liquid, then cool to 700 DEG C；
Prepare bromine gallium barium borate sodium seed crystal: by the mixed molten liquid that obtains with the speed slow cooling of 1.5 DEG C/h of temperature to room temperature,
Spontaneous crystallization obtains bromine gallium barium borate sodium seed crystal；
The crucible filling prepared mixed molten liquid is inserted in crystal growing furnace, then the NaBa that will obtain4Ga2B8O18Br3Seed crystal is solid
On seed rod, seed crystal from crystal growing furnace top, first on mixed molten liquid surface, preheat seed crystal 10 minutes, by seed crystal
Immerse in mixed molten liquid and carry out melt back, constant temperature 30 minutes, be cooled to 810 DEG C with the speed of 1 DEG C/h of temperature；
Again with the speed slow cooling of temperature 1 DEG C/day, not rotary seed crystal rod, after crystal growth arrives required yardstick, by crystal
Lift-off molten surface, is down to room temperature with temperature 20 DEG C/h speed, is then taken out from burner hearth by crystal, can obtain a size of
The NaBa of 36mm × 20mm × 18mm4Ga2B8O18Br3Nonlinear optical crystal.
Raw material barium nitrate in reaction equation can be replaced by brium carbonate or Barium monoxide or barium oxalate or barium hydroxide or barium bicarbonate,
Boric acid can be replaced by boron oxide.
Embodiment 3:
By reaction equation: 7BaO+2NaBr+BaBr2+2Ga2O3+16H3BO3→2NaBa4Ga2B8O18Br3+24H2O ↑ synthesis
NaBa4Ga2B8O18Br3Compound:
By BaO, NaBr, BaBr2、Ga2O3、H3BO3During 7:2:1:2:16 puts into mortar in molar ratio, mixing is also carefully ground,
It is then charged in the opening corundum crucible of Φ 100mm × 100mm, is compressed, put in Muffle furnace, be to slowly warm up to 550 DEG C,
Constant temperature 24 hours, takes out crucible after cooling, and now sample is more loose, takes out sample and re-grinds uniformly, then is placed in crucible
In, in temperature 800 DEG C constant temperature 48 hours again in Muffle furnace, it is drawn off, puts into mortar is smashed to pieces and grind and get final product
NaBa4Ga2B8O18Br3Compound, carries out X-ray analysis, gained X-ray spectrogram and bromine gallium barium borate sodium to this product
NaBa4Ga2B8O18Br3The X-ray spectrogram that mono-crystalline structures obtains is consistent；
NaBa by synthesis4Ga2B8O18Br3Compound single-phase polycrystal powder and flux LiBr NaBa in molar ratio4Ga2B8O18Br3:
LiBr=1:5 carries out mixture, loads in the opening platinum crucible of Φ 80mm × 80mm, with the heating rate of temperature 1-30 DEG C/h
It is heated to temperature to 880 DEG C, constant temperature 30 hours, obtain mixed molten liquid, then be down to temperature 720 DEG C；
Prepare bromine gallium barium borate sodium seed crystal: by the mixed molten liquid that obtains with the speed slow cooling of 2.5 DEG C/h of temperature to room temperature,
Spontaneous crystallization obtains bromine gallium barium borate sodium seed crystal；
The crucible filling prepared mixed molten liquid is inserted in crystal growing furnace, then the seed crystal of acquisition is fixed on seed rod,
Seed crystal from crystal growing furnace top, first preheats seed crystal 5 minutes on mixed molten liquid surface, and seed crystal is molten down to contact mixing
Liquid liquid level carries out melt back, constant temperature 5 minutes, is cooled to 820 DEG C with the speed of 5 DEG C/h of temperature；
Again with the speed slow cooling of temperature 3 DEG C/day, with the rotating speed rotary seed crystal rod of 30rpm, treat that crystal growth arrives required chi
After degree, by crystal lift-off molten surface, it is down to room temperature with temperature 30 DEG C/h speed, then crystal is taken out from burner hearth, i.e.
The NaBa of a size of 36mm × 40mm × 30mm can be obtained4Ga2B8O18Br3Nonlinear optical crystal.
Raw material Barium monoxide in reaction equation can be replaced by brium carbonate or barium nitrate or barium oxalate or barium hydroxide or barium bicarbonate,
Boric acid can be replaced by boron oxide.
Embodiment 4:
By reaction equation: 7Ba (OH)2+2NaBr+BaBr2+2Ga2O3+16H3BO3→2NaBa4Ga2B8O18Br3+31H2O ↑ compound:
By Ba (OH)2、NaBr、BaBr2、Ga2O3、H3BO3During 7:2:1:2:16 puts into mortar in molar ratio, mixing is the most careful
Grind, be then charged in the opening corundum crucible of Φ 100mm × 100mm, compressed, put in Muffle furnace, slowly heat up
To 550 DEG C, constant temperature 24 hours, take out crucible after cooling, now sample is more loose, takes out sample and re-grinds uniformly,
It is placed in again in crucible, in temperature 800 DEG C constant temperature 48 hours again in Muffle furnace, is drawn off, puts into and mortar is smashed to pieces grinding
Obtain NaBa4Ga2B8O18Br3Compound, carries out X-ray analysis, gained X-ray spectrogram and bromine gallium barium borate sodium to this product
NaBa4Ga2B8O18Br3The X-ray spectrogram that mono-crystalline structures obtains is consistent；
Then by the NaBa of synthesis4Ga2B8O18Br3Compound single-phase polycrystal powder and flux KBr-PbO 1:7 in molar ratio,
Carrying out mixture, wherein KBr Yu PbO mol ratio is 1:1, loads in the opening platinum crucible of Φ 80mm × 80mm, with temperature
The heating rate of 15 DEG C/h is heated to temperature 920 DEG C, constant temperature 30 hours, obtains mixed liquor, then is down to temperature 760 DEG C；
Prepare bromine gallium barium borate sodium seed crystal: by the mixed molten liquid that obtains with the speed slow cooling of 3 DEG C/h of temperature to room temperature,
Spontaneous crystallization obtains bromine gallium barium borate sodium seed crystal；
The crucible filling prepared mixed molten liquid is inserted in crystal growing furnace, then the NaBa that will obtain4Ga2B8O18Br3Seed crystal is solid
On seed rod, seed crystal from crystal growing furnace top, first on mixed molten liquid surface, preheat seed crystal 8 minutes, by seed crystal
Immerse in mixed molten liquid and carry out melt back, constant temperature 15 minutes, be cooled to 800 DEG C with the speed of 10 DEG C/h of temperature；
Again with the speed slow cooling of temperature 0.5 DEG C/day, with the rotating speed rotary seed crystal rod of 50rpm, treat that crystal growth arrives required
After yardstick, by crystal lift-off molten surface, it is down to room temperature with temperature 60 C/h speed, then crystal is taken out from burner hearth,
The NaBa of a size of 32mm × 42mm × 16mm can be obtained4Ga2B8O18Br3Nonlinear optical crystal.
Feed hydrogen Barium monoxide in reaction equation can be replaced by brium carbonate or barium nitrate or barium oxalate or Barium monoxide or barium bicarbonate,
Boric acid can be replaced by boron oxide.
Embodiment 5:
By reaction equation: 7Ba (HCO3)2+BaF2+22H3BO3→2Ba4B11O20F+14CO2↑+40H2O ↑ synthesis NaBa4Ga2B8O18Br3
Compound:
By Ba (HCO3)2、NaBr、BaBr2、Ga2O3、H3BO37:2:1:2:16 directly weighs raw material in molar ratio, will claim
The raw material taken and flux LiBr-PbO 1:8 in molar ratio, carry out mixture, and wherein LiBr Yu PbO mol ratio is 3:1,
Load in the opening platinum crucible of Φ 80mm × 80mm, be heated to temperature 900 DEG C, constant temperature with the heating rate of 20 DEG C/h of temperature
60 hours, obtain mixed molten liquid, then be down to temperature 755 DEG C；
Prepare bromine gallium barium borate sodium seed crystal: by the mixed molten liquid that obtains with the speed slow cooling of 3.5 DEG C/h of temperature to room temperature,
Spontaneous crystallization obtains bromine gallium barium borate sodium seed crystal；
The crucible filling prepared mixed molten liquid is inserted in crystal growing furnace, then the NaBa that will obtain4Ga2B8O18Br3Seed crystal is solid
On seed rod, seed crystal from crystal growing furnace top, first on mixed molten liquid surface, preheat seed crystal 25 minutes, by seed crystal
Carry out melt back, constant temperature 35 minutes down to contact mixed molten liquid liquid level, be cooled to 855 DEG C with the speed of 20 DEG C/h of temperature；
Again with the speed slow cooling of temperature 3 DEG C/day, rotate seed crystal crucible with the rotating speed of 5rpm, treat that crystal growth arrives required
After yardstick, by crystal lift-off molten surface, it is down to room temperature with temperature 1 DEG C/h speed, then crystal is taken out from burner hearth,
The NaBa of a size of 35mm × 25mm × 10mm can be obtained4Ga2B8O18Br3Nonlinear optical crystal.
Oxide spinel hydrogen barium in reaction equation can be replaced by brium carbonate or barium nitrate or barium oxalate or barium hydroxide or Barium monoxide,
Boric acid can be replaced by boron oxide.
Embodiment 6:
By reaction equation: 7BaCO3+2NaBr+BaBr2+2Ga2O3+8B2O3→2NaBa4Ga2B8O18Br3+7CO2↑ synthesis
NaBa4Ga2B8O18Br3Compound:
By BaCO3、NaBr、BaBr2、Ga2O3、B2O37:2:1:2:8 directly weighs raw material in molar ratio, former by weigh
Material and flux LiBr-PbO 1:6 in molar ratio carry out mixture, and wherein LiBr Yu PbO mol ratio is 3:2, load
In the opening platinum crucible of Φ 80mm × 80mm, being heated to temperature 820 DEG C with the heating rate of 25 DEG C/h of temperature, constant temperature 20 is little
Time, obtain mixed molten liquid, then be down to temperature 725 DEG C；
Prepare bromine gallium barium borate sodium seed crystal: by the mixed molten liquid that obtains with the speed slow cooling of 5 DEG C/h of temperature to room temperature,
Spontaneous crystallization obtains bromine gallium barium borate sodium seed crystal；
The crucible filling prepared mixed molten liquid is inserted in crystal growing furnace, then the NaBa that will obtain4Ga2B8O18Br3Seed crystal is solid
On seed rod from crystal growing furnace top seed crystal, first on mixed molten liquid surface, preheat seed crystal 20 minutes, amethyst soaked
Enter under liquid level, make seed crystal carry out melt back, constant temperature 35 minutes in mixed molten liquid, be cooled to 780 DEG C with the speed of 30 DEG C/h of temperature；
Again with the speed slow cooling of temperature 4 DEG C/day, with the rotating speed rotary seed crystal rod of 15rpm, treat that crystal growth arrives required chi
After degree, by crystals from molten surface, it is down to room temperature with temperature 15 DEG C/h speed, then crystal is taken out from burner hearth, i.e.
The NaBa of a size of 35mm × 25mm × 20mm can be obtained4Ga2B8O18Br3Nonlinear optical crystal.
Oxide spinel barium in reaction equation can be replaced by Barium monoxide or barium nitrate or barium oxalate or barium hydroxide or barium bicarbonate,
Boron oxide can be replaced by boric acid.
Embodiment 7
By reaction equation: 7Ba (NO3)2+2NaBr+BaBr2+2Ga2O3+8B2O3→2NaBa4Ga2B8O18Br3+13NO2↑+NO↑+
4O2↑ synthesis NaBa4Ga2B8O18Br3Compound
By Ba (NO3)2、NaBr、BaBr2、Ga2O3、B2O37:2:1:2:8 directly weighs raw material in molar ratio, former by weigh
Material and flux LiBr-H3BO31:5 carries out mixture, wherein LiBr and H in molar ratio3BO3Mol ratio is that 5:3 loads
In the opening platinum crucible of Φ 80mm × 80mm, being heated to temperature 1000 DEG C with the heating rate of 5 DEG C/h of temperature, constant temperature 80 is little
Time, obtain mixed molten liquid, then be down to temperature 760 DEG C；
Prepare bromine gallium barium borate sodium seed crystal: by the mixed molten liquid that obtains with the speed slow cooling of 10 DEG C/h of temperature to room temperature,
Spontaneous crystallization obtains bromine gallium barium borate sodium seed crystal；
The crucible filling prepared mixed molten liquid is inserted in crystal growing furnace, then the seed crystal of acquisition is fixed on seed rod,
Seed crystal from crystal growing furnace top, first preheats seed crystal 45 minutes on mixed molten liquid surface, by seed crystal down in mixed molten liquid,
Make seed crystal carry out melt back, constant temperature 25 minutes in mixed molten liquid, be cooled to 820 DEG C with the speed of temperature 50 C/h；
Lower the temperature with the speed of temperature 5 DEG C/day again, with the rotating speed rotary seed crystal rod of 30rpm, after crystal growth arrives required yardstick,
By crystal lift-off molten surface, it is down to room temperature with temperature 35 DEG C/h speed, then crystal is taken out from burner hearth, can obtain
The NaBa of a size of 26mm × 35mm × 20mm4Ga2B8O18Br3Nonlinear optical crystal.
Raw material barium nitrate in reaction equation can be replaced by barium bicarbonate or brium carbonate or barium oxalate or barium hydroxide or Barium monoxide,
Boron oxide can be replaced by boric acid.
Embodiment 8
By reaction equation: 7BaO+2NaBr+BaBr2+2Ga2O3+8B2O3→2NaBa4Ga2B8O18Br3Synthesis NaBa4Ga2B8O18Br3Change
Compound；
By BaO, NaBr, BaBr2、Ga2O3、B2O3During 7:2:1:2:8 puts into mortar in molar ratio, mixing is also carefully ground,
It is then charged in the opening corundum crucible of Φ 100mm × 100mm, is compressed, put in Muffle furnace, be to slowly warm up to 550 DEG C,
Constant temperature 24 hours, takes out crucible after cooling, and now sample is more loose, takes out sample and re-grinds uniformly, then is placed in crucible
In, in temperature 800 DEG C constant temperature 48 hours again in Muffle furnace, it is drawn off, puts into mortar is smashed to pieces and grind and get final product
NaBa4Ga2B8O18Br3Compound, carries out X-ray analysis, gained X-ray spectrogram and bromine gallium barium borate sodium to this product
NaBa4Ga2B8O18Br3The X-ray spectrogram that mono-crystalline structures obtains is consistent；
Then by the NaBa of synthesis4Ga2B8O18Br3Compound single-phase polycrystal powder and flux KBr-PbO 1:4 in molar ratio,
Carrying out mixture, wherein KBr Yu PbO mol ratio is 2:1, loads in the opening platinum crucible of Φ 80mm × 80mm, with temperature
The heating rate of 30 DEG C/h is heated to temperature 1050 DEG C, constant temperature 70 hours, obtains mixed molten liquid, then is down to temperature 725 DEG C；
Prepare bromine gallium barium borate sodium seed crystal: by the mixed molten liquid that obtains with the speed slow cooling of 4.0 DEG C/h of temperature to room temperature,
Spontaneous crystallization obtains bromine gallium barium borate sodium seed crystal；
The crucible filling prepared mixed molten liquid is inserted in crystal growing furnace, then the NaBa that will obtain4Ga2B8O18Br3Seed crystal is solid
On seed rod, seed crystal from crystal growing furnace top, first on mixed molten liquid surface, preheat seed crystal 55 minutes, by seed crystal
Carry out melt back, constant temperature 50 clock down to contact mixed molten liquid liquid level, be cooled to 820 DEG C with the speed of temperature 45 C/h；
Again with the speed slow cooling of temperature 0.8 DEG C/day, rotate seed crystal crucible with the rotating speed of 10rpm, treat that crystal growth is to institute
After needing yardstick, by crystals from molten surface, it is down to room temperature with temperature 5 DEG C/h speed, then crystal is taken out from burner hearth,
The NaBa of a size of 16mm × 25mm × 18mm can be obtained4Ga2B8O18Br3Nonlinear optical crystal.
Raw material Barium monoxide in reaction equation can be replaced by brium carbonate or barium bicarbonate or barium oxalate or barium hydroxide or barium nitrate,
Boron oxide can be replaced by boric acid.
Embodiment 9
By reaction equation: 7Ba (OH)2+2NaBr+BaBr2+2Ga2O3+8B2O3→2NaBa4Ga2B8O18Br3+7H2O ↑ synthesis
NaBa4Ga2B8O18Br3Compound:
By Ba (OH)2、NaBr、BaBr2、Ga2O3、B2O3During 7:2:1:2:8 puts into mortar in molar ratio, mixing is also carefully ground
Mill, is then charged in the opening corundum crucible of Φ 100mm × 100mm, is compressed, put in Muffle furnace, be to slowly warm up to
550 DEG C, constant temperature 24 hours, take out crucible after cooling, now sample is more loose, takes out sample and re-grinds uniformly, then
It is placed in crucible, in temperature 800 DEG C constant temperature 48 hours again in Muffle furnace, is drawn off, put into and mortar is smashed grinding i.e. to pieces
Obtain NaBa4Ga2B8O18Br3Compound, carries out X-ray analysis, gained X-ray spectrogram and bromine gallium barium borate sodium to this product
NaBa4Ga2B8O18Br3The X-ray spectrogram that mono-crystalline structures obtains is consistent；
Then by the NaBa of synthesis4Ga2B8O18Br3Compound single-phase polycrystal powder and flux LiBr-PbO 1:10 in molar ratio,
Carrying out mixture, LiBr Yu PbO mol ratio is 5:1, loads in the opening platinum crucible of Φ 80mm × 80mm, with 10 DEG C/h of temperature
Heating rate be heated to temperature 950 DEG C, constant temperature 45 hours, obtain mixed molten liquid, then be down to temperature 750 DEG C；
Prepare bromine gallium barium borate sodium seed crystal: by the mixed molten liquid that obtains with the speed slow cooling of 6.5 DEG C/h of temperature to room temperature,
Spontaneous crystallization obtains bromine gallium barium borate sodium seed crystal；
The crucible filling prepared mixed molten liquid is inserted in crystal growing furnace, then the NaBa that will obtain4Ga2B8O18Br3Seed crystal is solid
On seed rod, seed crystal from crystal growing furnace top, first on mixed molten liquid surface, preheat seed crystal 60 minutes, by seed crystal
Immerse in mixed molten liquid and carry out melt back, constant temperature 25 minutes, be cooled to 840 DEG C with the speed of 30 DEG C/h of temperature；
Again with the speed slow cooling of temperature 2 DEG C/day, with the rotating speed rotary seed crystal rod of 60rpm, treat that crystal growth arrives required chi
After degree, by crystals from molten surface, it is down to room temperature with temperature 80 DEG C/h speed, then crystal is taken out from burner hearth, i.e.
The NaBa of a size of 22mm × 32mm × 16mm can be obtained4Ga2B8O18Br3Nonlinear optical crystal.
Feed hydrogen Barium monoxide in reaction equation can be replaced by brium carbonate or barium bicarbonate or barium oxalate or barium nitrate or Barium monoxide,
Boron oxide can be replaced by boric acid.
Embodiment 10
By reaction equation: 7Ba (HCO3)2+2NaBr+BaBr2+2Ga2O3+8B2O3→2NaBa4Ga2B8O18Br3+14CO2↑+7H2O↑；Close
Become NaBa4Ga2B8O18Br3Compound:
By Ba (HCO3)2、NaBr、BaBr2、Ga2O3、B2O3During 7:2:1:2:8 puts into mortar in molar ratio, mixing is the youngest
Fine lapping, is then charged in the opening corundum crucible of Φ 100mm × 100mm, is compressed, put in Muffle furnace, slowly rise
Warm to 550 DEG C, constant temperature 24 hours, take out crucible after cooling, now sample is more loose, takes out sample and re-grinds uniformly,
It is placed in again in crucible, in temperature 800 DEG C constant temperature 48 hours again in Muffle furnace, is drawn off, puts into and mortar is smashed to pieces grinding
Obtain NaBa4Ga2B8O18Br3Compound, carries out X-ray analysis, gained X-ray spectrogram and bromine gallium barium borate sodium to this product
NaBa4Ga2B8O18Br3The X-ray spectrogram that mono-crystalline structures obtains is consistent；
NaBa by synthesis4Ga2B8O18Br3Compound single-phase polycrystal powder mixes with flux LiBr-PbO 1:6 in molar ratio
Joining, wherein LiBr Yu PbO mol ratio is 2:3, loads in the opening platinum crucible of Φ 80mm × 80mm, with 30 DEG C/h of temperature
Heating rate be heated to temperature 950 DEG C, constant temperature obtains mixed molten liquid for 70 hours, then is down to temperature 745 DEG C；
Prepare bromine gallium barium borate sodium seed crystal: by the mixed molten liquid that obtains with the speed slow cooling of 8.0 DEG C/h of temperature to room temperature,
Spontaneous crystallization obtains bromine gallium barium borate sodium seed crystal；
The crucible filling prepared mixed molten liquid is inserted in crystal growing furnace, then the NaBa that will obtain4Ga2B8O18Br3Seed crystal is solid
On seed rod, seed crystal from crystal growing furnace top, first on mixed molten liquid surface, preheat seed crystal 20 minutes, by amethyst
Immerse in mixed molten liquid and carry out melt back, constant temperature 60 minutes, be down to fast cooling to 845 DEG C with the speed of temperature 60 C/h；
Lower the temperature with the speed of temperature 3 DEG C/day again, with the rotating speed rotary seed crystal rod of 50rpm, after crystal growth arrives required yardstick,
By crystals from molten surface, it is down to room temperature with temperature 70 C/h speed, then crystal is taken out from burner hearth, can obtain
The NaBa of a size of 25mm × 25mm × 18mm4Ga2B8O18Br3Nonlinear optical crystal.
Oxide spinel hydrogen barium in reaction equation can be replaced by brium carbonate or barium hydroxide or barium oxalate or barium nitrate or Barium monoxide,
Boron oxide can be replaced by boric acid；
Embodiment 11
By reaction equation: 7BaC2O4+2NaBr+BaBr2+2Ga2O3+8B2O3→2NaBa4Ga2B8O18Br3+7CO2↑+7CO ↑ synthesis
NaBa4Ga2B8O18Br3Compound
By BaC2O4、NaBr、BaBr2、Ga2O3、B2O37:2:1:2:8 directly weighs raw material in molar ratio, the raw material that will weigh
With flux PbO-H3BO31:5 carries out mixture, wherein PbO and H in molar ratio3BO3Mol ratio is that 5:3 loads
In the opening platinum crucible of Φ 80mm × 80mm, being heated to temperature 820 DEG C with the heating rate of 25 DEG C/h of temperature, constant temperature 80 is little
Time, obtain mixed molten liquid, then be down to temperature 760 DEG C；
Prepare bromine gallium barium borate sodium seed crystal: by the mixed molten liquid that obtains with the speed slow cooling of 2 DEG C/h of temperature to room temperature,
Spontaneous crystallization obtains bromine gallium barium borate sodium seed crystal；
The crucible filling prepared mixed molten liquid is inserted in crystal growing furnace, then the seed crystal of acquisition is fixed on seed rod,
Seed crystal from crystal growing furnace top, first preheats seed crystal 45 minutes on mixed molten liquid surface, is immersed in mixed molten liquid by amethyst
Carry out melt back, constant temperature 55 minutes, be cooled to 780 DEG C with the speed of temperature 50 C/h；
Lower the temperature with the speed of temperature 5 DEG C/day again, with the rotating speed rotary seed crystal rod of 30rpm, after crystal growth arrives required yardstick,
By crystal lift-off molten surface, it is down to room temperature with temperature 20 DEG C/h speed, then crystal is taken out from burner hearth, can obtain
The NaBa of a size of 25mm × 22mm × 20mm4Ga2B8O18Br3Nonlinear optical crystal.
Raw material barium oxalate in reaction equation can be replaced by barium bicarbonate or barium nitrate or brium carbonate or barium hydroxide or Barium monoxide,
Boron oxide can be replaced by boric acid.
Embodiment 12
By the arbitrary NaBa of embodiment 1-12 gained4Ga2B8O18Br3Crystal is by the one piece of size of direction processing that matches
The frequency doubling device of 5mm × 5mm × 6mm, is placed on the position of 3 as shown in accompanying drawing 3, at room temperature, with adjusting Q Nd:YAG
Laser light source, incident wavelength is 1064nm, is the red of 1064nm by adjusting Q Nd:YAG laser instrument 1 to send wavelength
Outer light beam 2 injects NaBa4Ga2B8O18Br3Monocrystalline 3, produces the green frequency doubled light that wavelength is 532nm, and output intensity is equal
10 times of condition KDP, outgoing beam 4 containing infrared light and the green glow of 532nm that wavelength is 1064nm, filtered
Obtain, after 5 eliminations, the green laser that wavelength is 532nm.
Claims (5)
1. a compound bromine gallium barium borate sodium, it is characterised in that the chemical formula of this compound is NaBa4Ga2B8O18Br3, molecular weight 1326.00, use solid phase method to prepare bromine gallium barium borate sodium compound.
2. a bromine gallium barium borate sodium nonlinear optical crystal, it is characterised in that the chemical formula of this crystal is NaBa4Ga2B8O18Br3, molecular weight 1326.00, not there is symmetrical centre, belonging to tetragonal crystal system, space group P4 (2) nm, cell parameter is a=12.347 (17), b=12.347 (17), c=6.911 (19), V=1053 (3)3。
3. the preparation method of a bromine gallium barium borate sodium nonlinear optical crystal as claimed in claim 2, it is characterised in that using high temperature solution method growth crystal, concrete operations follow these steps to carry out:
A, it is brium carbonate, barium nitrate, Barium monoxide, barium hydroxide, barium bicarbonate or barium oxalate by containing barium compound；Barium bromide, sodium bromide, gallium oxide and boric acid or boron oxide are during 7:2:1:2:16-8 puts into mortar in molar ratio, mixing is also carefully ground, and is then charged in the opening corundum crucible of Φ 100mm × 100mm, puts in Muffle furnace, it is to slowly warm up to 550 DEG C, constant temperature 24 hours, takes out crucible after cooling, now sample is more loose, take out sample to re-grind uniformly, then be placed in crucible, in temperature 800 DEG C constant temperature 48 hours again in Muffle furnace, it is drawn off, puts into mortar to be smashed to pieces grind and i.e. obtain NaBa4Ga2B8O18Br3Compound, carries out X-ray analysis, gained X-ray spectrogram and bromine gallium barium borate sodium NaBa to this product4Ga2B8O18Br3The X-ray spectrogram that mono-crystalline structures obtains is consistent；
B, bromine gallium barium borate sodium compound single-phase polycrystalline powder step a obtained and flux are LiBr, LiBr-H3BO3、LiBr-PbO、H3BO3-PbO, LiBr-PbO or KBr-PbO 1:3-10 in molar ratio uniformly mixes, load in the opening platinum crucible of Φ 80mm × 80mm, be heated to temperature 820-1050 DEG C, constant temperature 5-80 hour with the heating rate of temperature 1-30 DEG C/h, obtain mixed molten liquid, then be cooled to 685-760 DEG C；
Or directly 7:2:1:2:16:3-10 weighs containing barium compound in molar ratio is brium carbonate, barium nitrate, Barium monoxide, barium hydroxide, barium bicarbonate or barium oxalate；Barium bromide, sodium bromide, gallium oxide and boric acid or boron oxide are LiBr, LiBr-H with flux3BO3、LiBr-PbO、H3BO3-PbO, LiBr-PbO or KBr-PbO uniformly mix, and load in the opening platinum crucible of Φ 80mm × 80mm, are heated to temperature 820-1050 DEG C, constant temperature 5-80 hour with the heating rate of temperature 1-30 DEG C/h, obtain mixed molten liquid, then be cooled to 685-760 DEG C；
C, preparing bromine gallium barium borate sodium seed crystal: mixed molten liquid step b obtained is slowly dropped to room temperature with the speed of temperature 0.5-10 DEG C/h, spontaneous crystallization obtains bromine gallium barium borate sodium seed crystal；
D, insert in crystal growing furnace by filling the crucible of mixed molten liquid that step b prepares, seed crystal step c obtained is fixed on seed rod, seed crystal from crystal growing furnace top, first preheating seed crystal 5-60 minute, seed crystal is carried out melt back in contact mixed molten liquid liquid level or immersion mixed molten liquid, constant temperature 5-60 minute, is down to 780-855 DEG C with the speed of temperature 1-60 DEG C/h；
E, again with temperature 0.1-5 DEG C/day speed slow cooling, the growth of crystal is carried out with 0～60rpm rotating speed rotary seed crystal rod, after required yardstick is arrived in crystal growth, by crystal lift-off mixed molten liquid surface, and it is down to room temperature with temperature 1-80 DEG C/h speed, then crystal is taken out from burner hearth, i.e. prepare bromine gallium barium borate sodium nonlinear optical crystal.
4. the preparation method of bromine gallium barium borate sodium nonlinear optical crystal as claimed in claim 3, it is characterised in that LiBr-H in step b3BO3LiBr and H in flux3BO3Mol ratio be 1-8:1-5；H3BO3H in-PbO flux3BO3It is 1-6:1-5 with the mol ratio of PbO；Bromide in LiBr-PbO, LiBr-PbO or KBr-PbO flux is 2-5:1-3 with the mol ratio of lead oxide.
5. a bromine gallium barium borate sodium nonlinear optical crystal as claimed in claim 2 purposes in preparation times frequency generator, upper frequency transducer, lower frequency transducer or optical parametric oscillator.
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| CN115467023A (en) * | 2022-10-13 | 2022-12-13 | 天津理工大学 | Compound lithium gallium iodine oxygen and sodium gallium iodine oxygen, lithium gallium iodine oxygen and sodium gallium iodine oxygen nonlinear optical crystal, and preparation method and application thereof |
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