CN103588218B - CsZn2B3O7Compound, CsZn2B3O7Nonlinear optical crystal and its preparation method and purposes - Google Patents
CsZn2B3O7Compound, CsZn2B3O7Nonlinear optical crystal and its preparation method and purposes Download PDFInfo
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Abstract
The present invention provides CsZn2B3O7Chemicals, CsZn2B3O7Nonlinear optical crystal and its production and use, is related to non-linear optical crystal material field；The compound is prepared using solid reaction process；CsZn2B3O7Crystal is free of symmetrical centre, belongs to rhombic system Cmc21Space group, cell parameter is Z=12；The CsZn2B3O7Nonlinear optical crystal can prepare its Centimeter Level monocrystalline using flux growth metrhod；CsZn2B3O7The frequency-doubling conversion efficiency of nonlinear optical crystal is about KH2PO41.5 times of crystal, its UV absorption cut-off side is about 218nm；CsZn2B3O7Crystal physicochemistry property is stable, hardness is moderate, it is easy to cuts, process, preserve and uses, and available for device for non-linear optical is made, opens up the nonlinear optics application of ultraviolet band.
Description
Technical field
The present invention relates to a kind of CsZn2B3O7Compound, CsZn2B3O7Nonlinear optical crystal, the CsZn2B3O7Crystal
Preparation method and the crystal are used for the purposes for making device for non-linear optical.
Background technology
The nonlinear optical effect of crystal refers to such a effect：When a branch of laser with certain polarization direction presses one
When determining direction by one block of nonlinear optical crystal, the frequency of the light beam will change.Crystalline substance with nonlinear optical effect
Body is referred to as nonlinear optical crystal.Using the nonlinear optical effect of crystal, second harmonic generator and upper and lower frequency can be made
The device for non-linear optical such as rate converter and optical parametric oscillator.The complete solid of frequency transformation is carried out using nonlinear optical crystal
State laser is a developing direction of following laser, and its key is to obtain outstanding nonlinear optical crystal.
At present, the nonlinear optical crystal applied to ultraviolet band mainly has2-BaB2O4（BBO）、LiB3O5（LBO）、
CsLiB6O10（CLBO）And K2Be2BO3F2（KBBF）Deng, but all there is respective weak point in them.For example, LBO birefringence
Rate is all smaller, it is impossible to realize the quadruple output of 1064nm wavelength lasers；BBO birefringence is bigger than normal, for 1064nm ripples
There is photorefractive effect during the quadruple output of long laser, limit its power output and beam quality；And CLBO easily deliquescence,
It is difficult to commercial applications；KBBF causes it to be difficult to obtain c to the big crystalline substance of thickness then due to its serious layer growth habit
Body.Therefore, it is still urgent and necessary to explore the new ultra-violet nonlinear optical crystal of excellent combination property.
It is theoretical according to anionic group, containing conjugation(the BO of key3)3-Group has relatively large microcosmic Clock Multiplier Factor,
As these (BO3)3-Group orientation can produce big macroscopical Clock Multiplier Factor when consistent；Meanwhile, its plane configuration is conducive to production
Larger birefringence is given birth to realize the phase matched of ultraviolet band；In addition, (BO3)3-Group has wider band gap, is conducive to purple
The transmission of outer light and the raising of threshold for resisting laser damage.Therefore, (BO3)3-Group is considered as that design synthesizes ultraviolet and deep ultraviolet
One of optimal group of nonlinear optical crystal.The currently the only crystal KBBF for being capable of direct frequency doubling output deep ultraviolet laser, its
Basic structure primitive is (BO3)3-Group.In KBBF crystal structures, by (BO3)3-With (BeO3F)5-The plane layer constructed it
Between pass through weak K+-F-Ionic bond is connected, and this causes KBBF crystal to show serious layer growth habit.
Therefore, a kind of new ultra-violet nonlinear optical material of inventor's design synthesis：Within this material, (ZnO4)6-On four sides
Body replaces (BeO3F)5-Tetrahedron and (BO3)3-Group constructs a kind of new plane layer [Zn together2BO5]∞；Meanwhile, utilize
(B3O6)3-Group serves as the connection medium of plane between layers to strengthen interlayer attachment force；In addition, introducing cation inserts layer
Between space and maintain charge balance.So, on the one hand due to (ZnO4)6-Tetrahedral microcosmic second order nonlinear optical effect
It can not ignore, its geometric superposition will cause resulting materials to have bigger macro non-linear optical effect；On the other hand, layer and layer
Between rely on (B3O6)3-Group is as connection medium, and interlayer connection is closer, and gained new material will overcome or mitigate significantly stratiform
Habit.Based on this, the present inventor completes the present invention on the basis of a large amount of explore.Crystal structure analysis and powder times
Frequency test etc. all shows that this design is practicable.
The content of the invention
An object of the present invention is to provide a kind of chemical formula for CsZn2B3O7Compound.
An object of the present invention is to provide a kind of CsZn2B3O7The preparation method of compound.
An object of the present invention is to provide a kind of CsZn2B3O7Nonlinear optical crystal.
An object of the present invention is to provide CsZn2B3O7The preparation method of crystal.
An object of the present invention is to provide CsZn2B3O7The purposes of nonlinear optical crystal.
Technical scheme is as follows：
（1）A kind of chemical formula is CsZn2B3O7Compound.
（2）A kind of CsZn2B3O7The preparation method of compound, it is characterised in that prepared using solid reaction process, the side
Method comprises the following steps：
It will contain after Cs compounds, compound containing Zn and boride alloy uniformly mix with stoichiometric proportion, to be not more than 150
DEG C/h speed is warming up to 500 DEG C and pre-sintering more than 24h, then cooling takes out grinding uniformly, then to be not more than 200 DEG C/h
800 DEG C of sintering more than 72h are warming up to, grinding more than 1 time is taken out in midway, you can obtain the compound of pure phase.
CsZn can be typically obtained the following is several2B3O7The reaction of compound:
(a)Cs2CO3+4ZnO+6H3BO3=2CsZn2B3O7+CO2↑+9H2O↑
(b)CsHCO3+2ZnCO3+3H3BO3=CsZn2B3O7+3CO2↑+5H2O↑
(c)CsOH+2Zn(OH)2+3H3BO3=CsZn2B3O7+7H2O↑
(d)Cs2CO3+4ZnO+3B2O3=2CsZn2B3O7+CO2↑
(e)4CsNO3+8ZnO+6B2O3=4CsZn2B3O7+4NO2↑+O2↑
（3）A kind of CsZn2B3O7Nonlinear optical crystal, its chemical formula is CsZn2B3O7, the crystal be free of symmetrical centre,
Belong to rhombic system Cmc21Space group, cell parameter is Z=12。
（4）One kind prepares CsZn2B3O7The method of nonlinear optical crystal, it is characterised in that using flux growth metrhod growth
CsZn2B3O7Nonlinear optical crystal, the fluxing agent is Cs2O-ZnF2-B2O3Fluxing agent system.
（5）According to（4）Method, it is characterised in that methods described comprises the following steps：
Will compound containing Cs, compound containing Zn, the ZnF2With boride alloy with mol ratio Cs：Zn：ZnF2:B=3-5：1-
2：3：8-12 is mixed and is ground uniform, is put into platinum crucible and is warming up to 700 DEG C of sintering and is down to room temperature after 1-2 days.Add and
The boride alloy of the weight such as boride alloy, melts after mixed grinding is uniform in crucible in raw material, on high-temperature fusant surface or molten
Crystal is grown in body.
According to the present invention, the condition of the growth crystal is, rate of temperature fall：0.2~5 DEG C/day, preferably 0.2~1 DEG C/day；
Rotating speed：0~50 rev/min, preferably 10~40 revs/min；Direction of rotation：Single direction rotation or bidirectional rotation（Such as reversible bidirectional rotation）.
According to the present invention, after after crystal growth yardstick needed for, seed rod is lifted, crystal is departed from liquid level, to be not more than
100 DEG C/h（Preferably smaller than 50 DEG C/h）Speed be cooled to room temperature, you can CsZn2B3O7Nonlinear optical crystal.
（6）According to（2）With（4）Method, be further characterized in that, the compound containing Cs be selected from cesium carbonate, caesium bicarbonate,
Cesium nitrate or cesium hydroxide；The compound containing Zn is selected from zinc oxide, zinc carbonate or zinc hydroxide；Contain B described in the chemical combination containing B
Compound is selected from H3BO3Or B2O3。
（7）According to（4）Method, it is characterised in that methods described also include to CsZn2B3O7Nonlinear optical crystal
Post processing：After crystal growth terminates, will crystal stay in growth furnace and annealed, to be not more than 100 DEG C/h（It is preferred that small
In 50 DEG C/h）Speed be down to room temperature.
（8）The CsZn of the present invention2B3O7The purposes of nonlinear optical crystal, it is characterised in that the application is included as non-
Linear optics device is used.
Preferably, prepared device for non-linear optical is included passes through at least one piece by least a branch of incidence electromagnetic radiation
CsZn2B3O7After nonlinear optical crystal, the device that at least a branch of frequency is different from the output radiation of incidence electromagnetic radiation is produced.
According to the crystallography data of crystal, crystal boule is oriented, cut by required angle, thickness and sectional dimension brilliant
Body, by crystal thang-kng mirror polish, you can used as device for non-linear optical.
The CsZn2B3O7Nonlinear optical crystal has that physical and chemical performance is stable, the moderate, mechanicalness that is difficult deliquescence, hardness
The advantages of can be good, not easily broken, easy to process and preserve；So the invention furthermore provides CsZn2B3O7Non-linear optical crystal
The purposes of body, it is the CsZn2B3O7Nonlinear optical crystal is used to prepare device for non-linear optical.
The CsZn of the present invention2B3O7Compound, nonlinear optical crystal of the compound and its production and use just like
Lower beneficial effect：
In the CsZn2B3O7The growing crystals of nonlinear optical crystal are easily grown up and transparent without inclusion enclave, with growth speed
Degree is very fast, cost is low, the advantages of be easily obtained large-size crystal；The CsZn obtained2B3O7Nonlinear optical crystal have compared with
Short UV absorption cut-off side, larger nonlinear optical effect, physical and chemical performance is stable, be difficult deliquescence, good mechanical property,
The advantages of easy to process and preservation；The CsZn2B3O7Nonlinear optical crystal can be used for making device for non-linear optical；The present invention
The device for non-linear optical that nonlinear optical crystal makes can be used in some military and civilian high-tech areas, such as laser-induced
Blind weapon, video disc recording, laser projection tv, optical oomputing and optical-fibre communications etc..
Brief description of the drawings
Fig. 1 is to use CsZn2B3O7A kind of fundamental diagram for typical device for non-linear optical that crystal is made.
Fig. 2 is CsZn of the invention2B3O7Polycrystal powder X ray diffracting spectrum is with being based on CsZn2B3O7Crystal structure is simulated
X ray diffracting spectrum.
Fig. 3 is CsZn of the invention2B3O7Crystal structure figure.
Wherein：1 is laser, and 2 be incoming laser beam, and 3 be that the CsZn with optical manufacturing is post-processed through crystal2B3O7It is brilliant
Body, 4 be produced laser beam, and 5 be optical filter.
1 CsZn is used to the present invention below in conjunction with the accompanying drawings2B3O7The device for non-linear optical that crystal makes is made specifically
It is bright.Light beam 2 is sent by laser 1 and injects CsZn2B3O7Crystal 3, produced outgoing beam 4 is by filter plate 5, so as to obtain
Required laser beam.The nonlinear optics laser can be that times frequency generator or upper and lower frequency converter or optical parameter are shaken
Swing device etc..
Embodiment
The present invention is further described with reference to embodiment and accompanying drawing.Those skilled in the art know that following embodiments are not
It is limiting the scope of the invention, any improvement made on the basis of the present invention and change are all in the protection model of the present invention
Within enclosing.
Embodiment 1
Prepare powdered CsZn2B3O7Compound.
Using solid reaction process, reaction equation is as follows：
Cs2CO3+4ZnO+6H3BO3=2CsZn2B3O7+CO2↑+9H2O↑
Above-mentioned three kinds of reagent inventorys：Cs2CO33.258 gram（0.01mol）, 3.256 grams of ZnO（0.04mol）、H3BO3
3.710 gram（0.06mol）.
Concrete operation step is：Reagent is weighed respectively by above-mentioned dosage, they are put into mortar, is mixed and is ground
It is even, it is then charged into 10mL corundum ceramic crucible, is compacted into, be put into Muffle furnace, 500 is warming up to 50 DEG C/h speed
DEG C and constant temperature 24h.It is down to taking-up sample after room temperature to re-grind uniformly, then is placed in crucible and compacting, with 100 in Muffle furnace
DEG C/h speed is warming up to 800 DEG C of sintering 72h, grinding 1 time is taken out in midway, you can pure phase CsZn2B3O7Compound.Such as Fig. 2
Shown, its x-ray diffractogram of powder spectrum is consistent with the collection of illustrative plates according to obtained by the fitting of its mono-crystalline structures.
Embodiment 2
Prepare powdered CsZn2B3O7Compound.
Using solid reaction process, reaction equation is as follows：
CsHCO3+2ZnCO3+3H3BO3=CsZn2B3O7+3CO2↑+5H2O↑
Above-mentioned three kinds of reagent inventorys：CsHCO31.939 gram（0.01mol）、ZnCO32.508 gram（0.02mol）、
H3BO31.855 gram（0.03mol）.
Concrete operation step is：Reagent is weighed respectively by above-mentioned dosage, they are put into mortar, is mixed and is ground
It is even, it is then charged into 10mL corundum ceramic crucible, is compacted into, be put into Muffle furnace, is warming up to 100 DEG C/h speed
500 DEG C and constant temperature 24h.Be down to after room temperature and take out sample and re-grind uniformly, then be placed in crucible and compacting, in Muffle furnace with
150 DEG C/h speed is warming up to 800 DEG C of sintering 72h, and grinding 1 time is taken out in midway, you can obtain the CsZn of pure phase2B3O7Compound.
Embodiment 3
Prepare powdered CsZn2B3O7Compound.
Using solid reaction process, reaction equation is as follows：
CsOH+2Zn(OH)2+3H3BO3=CsZn2B3O7+7H2O↑
Above-mentioned three kinds of reagent inventorys：1.499 grams of CsOH（0.01mol）、Zn(OH)21.988 gram（0.02mol）、
H3BO31.855 gram（0.03mol）.
Concrete operation step is：Reagent is weighed respectively by above-mentioned dosage, they are put into mortar, is mixed and is ground
It is even, it is then charged into 10mL corundum ceramic crucible, is compacted into, be put into Muffle furnace, is warming up to 150 DEG C/h speed
500 DEG C and constant temperature 24h.Be down to after room temperature and take out sample and re-grind uniformly, then be placed in crucible and compacting, in Muffle furnace with
200 DEG C/h speed is warming up to 800 DEG C of sintering 120h, and midway takes out grinding 2 times, produces the CsZn of pure phase2B3O7Compound.
Embodiment 4
Prepare powdered CsZn2B3O7Compound.
Using solid reaction process, reaction equation is as follows：
Cs2CO3+4ZnO+3B2O3=2CsZn2B3O7+CO2↑
Above-mentioned three kinds of reagent inventorys：Cs2CO33.258 gram（0.01mol）, 3.256 grams of ZnO（0.04mol）、B2O3
2.089 gram（0.03mol）.
Concrete operation step is：Reagent is weighed respectively by above-mentioned dosage, they are put into mortar, is mixed and is ground
It is even, it is then charged into 10mL corundum ceramic crucible, is compacted into, be put into Muffle furnace, is warming up to 150 DEG C/h speed
500 DEG C and constant temperature 24h.Be down to after room temperature and take out sample and re-grind uniformly, then be placed in crucible and compacting, in Muffle furnace with
200 DEG C/h speed is warming up to 800 DEG C of sintering 120h, and midway takes out grinding 2 times, produces the CsZn of pure phase2B3O7Compound.
Embodiment 5
Prepare powdered CsZn2B3O7Compound.
Using solid reaction process, reaction equation is as follows：
4CsNO3+8ZnO+6B2O3=4CsZn2B3O7+4NO2↑+O2↑
Above-mentioned three kinds of reagent inventorys：CsNO33.898 gram（0.02mol）, 3.256 grams of ZnO（0.04mol）、B2O3
2.089 gram（0.03mol）.
Concrete operation step is：Reagent is weighed respectively by above-mentioned dosage, they are put into mortar, is mixed and is ground
It is even, it is then charged into 10mL corundum ceramic crucible, is compacted into, be put into Muffle furnace, is warming up to 100 DEG C/h speed
500 DEG C and constant temperature 24h.Be down to after room temperature and take out sample and re-grind uniformly, then be placed in crucible and compacting, in Muffle furnace with
150 DEG C/h speed is warming up to 800 DEG C of sintering 120h, and midway takes out grinding 2 times, produces the CsZn of pure phase2B3O7Compound.
Embodiment 6
Using flux growth metrhod, with Cs2O-ZnF2-B2O3Fluxing agent system grows CsZn2B3O7Crystal.
Weigh 162.9 grams（0.50mol）Cs2CO3, 32.6 grams（0.40mol）ZnO, 62.0 grams（0.60 mol）ZnF2With
74.2 grams（1.20mol）H3BO3, after mixed grinding is uniform, load in batches Opening platinum crucible
In.700 DEG C of simultaneously constant temperature 2 days are warming up to 100 DEG C/h speed in Muffle furnace, room temperature is then cooled to the furnace.Take out sintering
74.2 grams of product and addition afterwards（1.20mol）H3BO3, it is put into after grinding is uniformOpening platinum earthenware
Crucible, is warming up to 1000 DEG C of fusings in vertical crystal growing furnace and constant temperature 10h is so that melt is uniformed.With 4 DEG C/h speed
It is cooled to 800 DEG C, CsZn2B3O7Crystal separates out in bath surface, then is cooled to room temperature with 50 DEG C/h speed.Pick out transparent
Bulk crystals and powder x-ray diffraction analysis are carried out to it, it was demonstrated that gained crystal is CsZn2B3O7Crystal.
Gained crystal mass is cut compared with good part as seed crystal, raw material heats up again and melted, is then cooled fast to full
With more than temperature 10 DEG C.Slowly the seed rod equipped with seed crystal is stretched into the melt of crucible, and starts turning for seed rod upper end
Dynamic device, slewing rate is 25 revs/min.After constant temperature half an hour, fast cooling to saturation temperature, then with the speed of 0.5 DEG C/day
Cooling.After size, lift seed rod needed for after crystal growth, crystal is departed from liquid level, will crystal stay and anneal in a furnace
And room temperature is cooled to 20 DEG C/h of speed, you can obtain the CsZn of Centimeter Level2B3O7Crystal.
Embodiment 7
Using flux growth metrhod, with Cs2O-ZnF2-B2O3Fluxing agent system grows CsZn2B3O7Crystal.
Weigh 97.7 grams（0.30mol）Cs2CO3, 16.3 grams（0.20mol）ZnO, 62.0 grams（0.60mol）ZnF2With 49.5
Gram（0.80mol）H3BO3, after mixed grinding is uniform, load in batchesOpening platinum crucible in.
700 DEG C of simultaneously constant temperature 1 days are warming up to 100 DEG C/h speed in Muffle furnace, room temperature is then cooled to the furnace.Take out product after sintering
And add 49.5 grams（0.80mol）H3BO3, it is put into after grinding is uniformOpening platinum crucible,
1000 DEG C of fusings are warming up in vertical crystal growing furnace and constant temperature 20h is so that melt is uniformed.It is cooled fast to saturation temperature
10 DEG C of the above.Slowly the seed rod equipped with seed crystal is stretched into the melt of crucible, and starts the tumbler of seed rod upper end,
Slewing rate is 25 revs/min.After constant temperature half an hour, then fast cooling to saturation temperature is cooled with the speed of 0.5 DEG C/day.Treat
Crystal growth after size, lifts seed rod needed for, crystal is departed from liquid level, will crystal stay annealing in a furnace and with 20
DEG C/h speed be cooled to room temperature, you can Centimeter Level CsZn2B3O7Crystal.
Embodiment 8
Using flux growth metrhod, with Cs2O-ZnF2-B2O3Fluxing agent system grows CsZn2B3O7Crystal.
Weigh 162.9 grams（0.50mol）Cs2CO3, 19.9 grams（0.20mol）Zn(OH)2, 62.0 grams（0.60mol）ZnF2
With 61.8 grams（1.00mol）H3BO3, after mixed grinding is uniform, load in batches Opening platinum crucible
In.700 DEG C of simultaneously constant temperature 2 days are warming up to 150 DEG C/h speed in Muffle furnace, room temperature is then cooled to the furnace.Take out sintering
61.8 grams of product and addition afterwards（1.00mol）H3BO3, it is put into after grinding is uniformOpening platinum earthenware
Crucible, is warming up to 1000 DEG C of fusings in vertical crystal growing furnace and constant temperature 20h is so that melt is uniformed.It is cooled fast to saturation
More than temperature 10 DEG C.Slowly the seed rod equipped with seed crystal is stretched into the melt of crucible, and starts the rotation of seed rod upper end
Device, slewing rate is 25 revs/min.After constant temperature half an hour, then fast cooling to saturation temperature is dropped with the speed of 0.5 DEG C/day
Temperature.After size, lift seed rod needed for after crystal growth, crystal is departed from liquid level, will crystal stay and anneal in a furnace simultaneously
Room temperature is cooled to 20 DEG C/h of speed, you can obtain the CsZn of Centimeter Level2B3O7Crystal.
Above method is used to obtain CsZn of the size for Centimeter Level2B3O7Nonlinear optical crystal；Use large scale earthenware
Crucible, and extend growth period, then it can obtain the CsZn of corresponding large-size2B3O7Crystal.
Through single-crystal X-ray diffraction analysis, the CsZn prepared by above-described embodiment 5-62B3O7Crystal is free of
Symmetrical centre, belongs to rhombic system Cmc21Space group, cell parameter is Z=12.Fig. 3 is the CsZn2B3O7The structural representation of crystal.
Embodiment 9
By the CsZn of the gained of embodiment 62B3O7Nonlinear optical crystal passes through spectrum test, the UV absorption of the crystal
It is about 218nm to end side, and is passed through in 218-2500nm wave-length coverages；The crystal is not easily broken, it is easy to cut, polish plus
Work and preservation, and not deliquescence；By the CsZn of the gained of embodiment 52B3O7Nonlinear optical crystal, is placed on the shown device of accompanying drawing 1
At position marked as 3, at room temperature, with tune QNd:YAG laser makees fundamental frequency light source, and incident wavelength is 1064nm near-infrared
Light, output wavelength is 532nm green laser, and laser intensity is approximately equivalent to KDP (KH2PO4) 1.5 times；By the gained of embodiment 5
Li4Sr(BO3)2Nonlinear optical crystal, is placed at position of the shown device of accompanying drawing 1 marked as 3, at room temperature, uses 532nm
The green (light) laser of wavelength makees fundamental frequency light source, and incident wavelength is 532nm green glow, and output wavelength is 266nm Ultra-Violet Laser, is swashed
Luminous intensity is approximately equivalent to 1/3 times of BBO.
Claims (4)
1. one kind prepares CsZn2B3O7The method of nonlinear optical crystal, it is characterised in that using flux growth metrhod growth
CsZn2B3O7Nonlinear optical crystal, the fluxing agent is Cs2O-ZnF2-B2O3Fluxing agent system.
2. according to the method described in claim 1, it is characterised in that methods described comprises the following steps：Cs compounds will be contained, contained
Zn compounds, ZnF2With boride alloy with mol ratio Cs：Zn：ZnF2:B=3-5：1–2：3：8-12 mix and grind uniform, put
Enter to be warming up to 700 DEG C of sintering in platinum crucible and be down to room temperature after 1-2 day, add and contain Bization with the weight such as boride alloy in raw material
Compound, melts in crucible after mixed grinding is uniform, crystal is grown in high-temperature fusant surface or melt.
3. method according to claim 2, is further characterized in that, the compound containing Cs be selected from cesium carbonate, caesium bicarbonate,
Cesium nitrate or cesium hydroxide；The compound containing Zn is selected from zinc oxide, zinc carbonate or zinc hydroxide；The boride alloy is selected from
H3BO3Or B2O3。
4. method according to claim 2, it is characterised in that methods described also includes to CsZn2B3O7Nonlinear optical crystal
Post processing：After crystal growth terminates, will crystal stay in growth furnace and annealed, dropped with the speed for being not more than 100 DEG C/h
To room temperature.
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