CN103588218A - CsZn2B3O7 compound, CsZn2B3O7 nonlinear optical crystal as well as preparation method and application of CsZn2B3O7 nonlinear optical crystal - Google Patents

CsZn2B3O7 compound, CsZn2B3O7 nonlinear optical crystal as well as preparation method and application of CsZn2B3O7 nonlinear optical crystal Download PDF

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CN103588218A
CN103588218A CN201310493310.7A CN201310493310A CN103588218A CN 103588218 A CN103588218 A CN 103588218A CN 201310493310 A CN201310493310 A CN 201310493310A CN 103588218 A CN103588218 A CN 103588218A
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罗军华
赵三根
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Fujian Institute of Research on the Structure of Matter of CAS
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Abstract

The present invention provides CsZn2B3O7 chemicals, CsZn2B3O7 nonlinear optical crystal and its preparation method and application, is related to non-linear optical crystal material field; The compound is prepared using solid reaction process; CsZn2B3O7 crystal is free of symmetrical centre, belongs to rhombic system Cmc21 space group, cell parameter is
Figure DEST_PATH_DDA0000416061360000011
Figure DEST_PATH_DDA0000416061360000012
Z=12; , which can prepare its Centimeter Level monocrystalline using flux growth metrhod; The frequency-doubling conversion efficiency of CsZn2B3O7 nonlinear optical crystal is about 1.5 times of KH2PO4 crystal, and it is about 218nm that UV absorption, which ends side,; CsZn2B3O7 crystal physicochemistry property is stable, hardness is moderate, and easy to cut, processing is saved and used, and can be used for making device for non-linear optical, opens up the nonlinear optics application of ultraviolet band.

Description

CsZn 2b 3o 7compound, CsZn 2b 3o 7non-linear optic crystal and method for making thereof and purposes
Technical field
The present invention relates to a kind of CsZn 2b 3o 7compound, CsZn 2b 3o 7non-linear optic crystal, this CsZn 2b 3o 7the preparation method of crystal and this crystal purposes for making device for non-linear optical.
Background technology
The non-linear optical effect of crystal refers to a kind of like this effect: when a branch of laser with certain polarization direction passes through a non-linear optic crystal by certain orientation, the frequency of this light beam will change.The crystal with non-linear optical effect is called non-linear optic crystal.Utilize the non-linear optical effect of crystal, can make the device for non-linear optical such as second harmonic generator and upper and lower frequency converter and optical parametric oscillator.The all solid state laser that utilizes non-linear optic crystal to carry out frequency transformation is a developing direction of following laser apparatus, and its key is to obtain outstanding non-linear optic crystal.
At present, the non-linear optic crystal that is applied to ultraviolet band mainly contains 2-BaB 2o 4(BBO), LiB 3o 5(LBO), CsLiB 6o 10and K (CLBO) 2be 2bO 3f 2etc., but they all exist weak point separately (KBBF).For example, the degree of birefringence of LBO is all smaller, can not realize the quadruple output of 1064nm wavelength laser; The degree of birefringence of BBO is bigger than normal, while exporting for the quadruple of 1064nm wavelength laser, has photorefractive effect, has limited its output rating and beam quality; And CLBO deliquescence is very easily difficult to realize commercial applications; KBBF, due to its serious layer growth habit, causes it to be difficult to obtain c to the large crystal of thickness.Therefore it is urgent and necessary that the new ultra-violet non-linear optic crystal of, exploring excellent combination property remains.
Theoretical according to anionic group, containing conjugation
Figure BDA0000398740680000011
(the BO of key 3) 3-group has relatively large microcosmic Clock Multiplier Factor, as these (BO 3) 3-when group orientation is consistent, can produce large macroscopical Clock Multiplier Factor; Meanwhile, its plane configuration is conducive to produce larger double refraction to realize the phase matched of ultraviolet band; In addition, (BO 3) 3-group has wider band gap, is conducive to seeing through and the raising of threshold for resisting laser damage of UV-light.Therefore, (BO 3) 3-group is considered to one of best group designing synthetic ultraviolet and deep ultraviolet nonlinear optical crystal.Current unique crystal KBBF that can direct frequency doubling output deep ultraviolet laser, its basic structure primitive is (BO 3) 3-group.In KBBF crystalline structure, by (BO 3) 3-with (BeO 3f) 5-between the plane layer of constructing, pass through weak K +-F -ionic linkage connects, and this causes KBBF crystal to present serious layer growth habit.
Therefore, contriver designs synthetic a kind of new ultra-violet nonlinear optical material: in this material, and (ZnO 4) 6-tetrahedron replaces (BeO 3f) 5-tetrahedron and (BO 3) 3-group is constructed a kind of new plane layer [Zn together 2bO 5] ∞; Meanwhile, utilize (B 3o 6) 3-group serves as plane connection medium between layers with connection power between enhancement layer; In addition, introducing positively charged ion inserts bedding void and maintains charge balance.So, on the one hand due to (ZnO 4) 6-tetrahedral microcosmic second order nonlinear optical effect be can not ignore, and its geometric superposition will cause resulting materials to have larger macro non-linear optical effect; On the other hand, rely between layers (B 3o 6) 3-group is as connecting medium, and interlayer connects tightr, and gained novel material will overcome or greatly alleviate layer growth habit.Based on this, the inventor, on a large amount of bases of exploring, has completed the present invention.Crystal structure analysis and powder frequency doubling test etc. all show that this design is practicable.
Summary of the invention
It is CsZn that one of object of the present invention is to provide a kind of chemical formula 2b 3o 7compound.
One of object of the present invention is to provide a kind of CsZn 2b 3o 7the preparation method of compound.
One of object of the present invention is to provide a kind of CsZn 2b 3o 7non-linear optic crystal.
One of object of the present invention is to provide CsZn 2b 3o 7the preparation method of crystal.
One of object of the present invention is to provide CsZn 2b 3o 7the purposes of non-linear optic crystal.
Technical scheme of the present invention is as follows:
(1) a kind of chemical formula is CsZn 2b 3o 7compound.
(2) a kind of CsZn 2b 3o 7the preparation method of compound, is characterized in that, adopts solid reaction process preparation, and described method comprises the steps:
After evenly mixing with stoichiometric ratio containing Cs compound, containing Zn compound and boride alloy, to be not more than the speed of 150 ℃/h, be warmed up to 500 ℃ also more than presintering 24h, then cooling is taken out and is ground evenly, again to be not more than more than 200 ℃/h is warmed up to 800 ℃ of sintering 72h, take out to grind more than 1 time midway, get final product to obtain this compound of pure phase.
Below severally typically can obtain CsZn 2b 3o 7the reaction of compound:
(a)Cs 2CO 3+4ZnO+6H 3BO 3=2CsZn 2B 3O 7+CO 2↑+9H 2O↑
(b)CsHCO 3+2ZnCO 3+3H 3BO 3=CsZn 2B 3O 7+3CO 2↑+5H 2O↑
(c)CsOH+2Zn(OH) 2+3H 3BO 3=CsZn 2B 3O 7+7H 2O↑
(d)Cs 2CO 3+4ZnO+3B 2O 3=2CsZn 2B 3O 7+CO 2↑
(e)4CsNO 3+8ZnO+6B 2O 3=4CsZn 2B 3O 7+4NO 2↑+O 2↑
(3) a kind of CsZn 2b 3o 7non-linear optic crystal, its chemical formula is CsZn 2b 3o 7, this crystal, containing symmetry centre, does not belong to rhombic system Cmc2 1spacer, unit cell parameters is
Figure BDA0000398740680000032
z=12.
(4) a kind of CsZn for preparing 2b 3o 7the method of non-linear optic crystal, is characterized in that, adopts flux method growth CsZn 2b 3o 7non-linear optic crystal, described fusing assistant is Cs 2o-ZnF 2-B 2o 3fusing assistant system.
(5) according to the method for (4), it is characterized in that, described method comprises the steps:
By described containing Cs compound, containing Zn compound, ZnF 2with boride alloy with mol ratio Cs:Zn:ZnF 2: B=3-5:1-2:3:8-12 mixes and grinds evenly, puts into after platinum crucible is warming up to 700 ℃ of sintering 1-2 days and is down to room temperature.Add again with raw material in the heavy boride alloy such as boride alloy, mixed grinding melts after evenly in crucible, growing crystal in high-temperature fusant surface or melt.
According to the present invention, the condition of described growing crystal is, rate of temperature fall: 0.2～5 ℃/day, and preferably 0.2～1 ℃/day; Rotating speed: 0～50 rev/min, preferably 10～40 revs/min; Sense of rotation: single direction rotation or bidirectional rotation (as reversible bidirectional rotation).
According to the present invention, after crystal grows into required yardstick, promote seed rod, make crystal depart from liquid level, to be not more than the speed of 100 ℃/h (being preferably less than 50 ℃/h), be cooled to room temperature, get final product to obtain CsZn 2b 3o 7non-linear optic crystal.
(6) according to the method for (2) and (4), be further characterized in that, the described Cs compound that contains is selected from cesium carbonate, cesium bicarbonate, cesium nitrate or cesium hydroxide; The described Zn compound that contains is selected from zinc oxide, zinc carbonate or zinc hydroxide; Describedly containing boride alloy described in B chemical combination, be selected from H 3bO 3or B 2o 3.
(7) according to the method for (4), it is characterized in that, described method also comprises CsZn 2b 3o 7the aftertreatment of non-linear optic crystal: after crystal growth finishes, will crystal stay in growth furnace and anneal, be down to room temperature to be not more than the speed of 100 ℃/h (being preferably less than 50 ℃/h).
(8) CsZn of the present invention 2b 3o 7the purposes of non-linear optic crystal, is characterized in that, described application comprises as device for non-linear optical to be used.
Preferably, prepared device for non-linear optical comprises at least a branch of incidence electromagnetic radiation by least one CsZn 2b 3o 7after non-linear optic crystal, produce the device that at least a branch of frequency is different from the output radiation of incidence electromagnetic radiation.
According to the crystallography data of crystal, crystal blank is directed, by required angle, thickness and sectional dimension sliced crystal, by the logical light mirror polish of crystal, can be used as device for non-linear optical and use.
This CsZn 2b 3o 7non-linear optic crystal has that physical and chemical performance stablizes, is difficult for that deliquescence, hardness are moderate, good mechanical property, not easily broken, be easy to the advantages such as processing and preservation; So this invention also further provides CsZn 2b 3o 7the purposes of non-linear optic crystal, it is this CsZn 2b 3o 7non-linear optic crystal is for the preparation of device for non-linear optical.
CsZn of the present invention 2b 3o 7non-linear optic crystal of compound, this compound and its production and use has following beneficial effect:
At this CsZn 2b 3o 7the growing crystals of non-linear optic crystal is easily grown up and is transparent in inclusion, has that the speed of growth is very fast, cost is low, be easy to obtain the advantages such as large-size crystal; The CsZn obtaining 2b 3o 7non-linear optic crystal has shorter uv-absorbing cut-off limit, larger non-linear optical effect, physical and chemical performance stablized, is difficult for deliquescence, good mechanical property, is easy to the advantages such as processing and preservation; This CsZn 2b 3o 7non-linear optic crystal can be used for making device for non-linear optical; The device for non-linear optical that non-linear optic crystal of the present invention is made can be used in some military and civilian high-tech areas, such as blinding laser weapons, video disc recording, laser projection tv, photometry calculation and optical-fibre communications etc.
Accompanying drawing explanation
Fig. 1 uses CsZn 2b 3o 7the fundamental diagram of a kind of typical device for non-linear optical that crystal is made.
Fig. 2 is CsZn of the present invention 2b 3o 7polycrystal powder X ray diffracting spectrum with based on CsZn 2b 3o 7the X ray diffracting spectrum of crystalline structure simulation.
Fig. 3 is CsZn of the present invention 2b 3o 7crystalline structure figure.
Wherein: the 1st, laser apparatus, the 2nd, incoming laser beam, the 3rd, through the CsZn of crystal aftertreatment and optics processing 2b 3o 7crystal, the 4th, the laser beam producing, the 5th, spectral filter.
Below in conjunction with accompanying drawing 1, the present invention is adopted to CsZn 2b 3o 7the device for non-linear optical that crystal is made elaborates.By laser apparatus 1, send light beam 2 and inject CsZn 2b 3o 7 crystal 3, the outgoing beam 4 producing passes through filter plate 5, thereby obtains needed laser beam.This nonlinear optics laser apparatus can be frequency multiplication producer or upper and lower frequency converter or optical parametric oscillator etc.
Embodiment
Below in conjunction with embodiment and accompanying drawing, further describe the present invention.Those skilled in the art know, and following embodiment is not limiting the scope of the invention, and any improvement of making on basis of the present invention and variation are all within protection scope of the present invention.
Embodiment 1
Prepare Powdered CsZn 2b 3o 7compound.
Adopt solid reaction process, reaction equation is as follows:
Cs 2CO 3+4ZnO+6H 3BO 3=2CsZn 2B 3O 7+CO 2↑+9H 2O↑
Above-mentioned three kinds of reagent charging capacity: Cs 2cO 33.258 grams (0.01mol), ZnO 3.256 grams of (0.04mol), H 3bO 33.710 grams (0.06mol).
Concrete operation step is: by above-mentioned dosage, take respectively reagent, they are put into mortar, mix and grind evenly, then pack in the corundum ceramic crucible of 10mL, by its compacting, put into retort furnace, with the speed of 50 ℃/h, be warming up to 500 ℃ and constant temperature 24h.Be down to and take out sample after room temperature and again grind evenly, then be placed in crucible and compacting, the speed with 100 ℃/h in retort furnace is warmed up to 800 ℃ of sintering 72h, takes out and grinds 1 time midway, gets final product to obtain the CsZn of pure phase 2b 3o 7compound.As shown in Figure 2, its x-ray diffractogram of powder spectrum is with consistent according to the collection of illustrative plates of its single crystal structure matching gained.
Embodiment 2
Prepare Powdered CsZn 2b 3o 7compound.
Adopt solid reaction process, reaction equation is as follows:
CsHCO 3+2ZnCO 3+3H 3BO 3=CsZn 2B 3O 7+3CO 2↑+5H 2O↑
Above-mentioned three kinds of reagent charging capacity: CsHCO 31.939 grams (0.01mol), ZnCO 32.508 grams (0.02mol), H 3bO 31.855 grams (0.03mol).
Concrete operation step is: by above-mentioned dosage, take respectively reagent, they are put into mortar, mix and grind evenly, then pack in the corundum ceramic crucible of 10mL, by its compacting, put into retort furnace, with the speed of 100 ℃/h, be warming up to 500 ℃ and constant temperature 24h.Be down to and take out sample after room temperature and again grind evenly, then be placed in crucible and compacting, the speed with 150 ℃/h in retort furnace is warmed up to 800 ℃ of sintering 72h, takes out and grinds 1 time midway, gets final product to obtain the CsZn of pure phase 2b 3o 7compound.
Embodiment 3
Prepare Powdered CsZn 2b 3o 7compound.
Adopt solid reaction process, reaction equation is as follows:
CsOH+2Zn(OH) 2+3H 3BO 3=CsZn 2B 3O 7+7H 2O↑
Above-mentioned three kinds of reagent charging capacity: CsOH 1.499 grams of (0.01mol), Zn (OH) 21.988 grams (0.02mol), H 3bO 31.855 grams (0.03mol).
Concrete operation step is: by above-mentioned dosage, take respectively reagent, they are put into mortar, mix and grind evenly, then pack in the corundum ceramic crucible of 10mL, by its compacting, put into retort furnace, with the speed of 150 ℃/h, be warming up to 500 ℃ and constant temperature 24h.Be down to and take out sample after room temperature and again grind evenly, then be placed in crucible and compacting, the speed with 200 ℃/h in retort furnace is warmed up to 800 ℃ of sintering 120h, takes out and grinds 2 times midway, obtains the CsZn of pure phase 2b 3o 7compound.
Embodiment 4
Prepare Powdered CsZn 2b 3o 7compound.
Adopt solid reaction process, reaction equation is as follows:
Cs 2CO 3+4ZnO+3B 2O 3=2CsZn 2B 3O 7+CO 2↑
Above-mentioned three kinds of reagent charging capacity: Cs 2cO 33.258 grams (0.01mol), ZnO 3.256 grams of (0.04mol), B 2o 32.089 grams (0.03mol).
Concrete operation step is: by above-mentioned dosage, take respectively reagent, they are put into mortar, mix and grind evenly, then pack in the corundum ceramic crucible of 10mL, by its compacting, put into retort furnace, with the speed of 150 ℃/h, be warming up to 500 ℃ and constant temperature 24h.Be down to and take out sample after room temperature and again grind evenly, then be placed in crucible and compacting, the speed with 200 ℃/h in retort furnace is warmed up to 800 ℃ of sintering 120h, takes out and grinds 2 times midway, obtains the CsZn of pure phase 2b 3o 7compound.
Embodiment 5
Prepare Powdered CsZn 2b 3o 7compound.
Adopt solid reaction process, reaction equation is as follows:
4CsNO 3+8ZnO+6B 2O 3=4CsZn 2B 3O 7+4NO 2↑+O 2↑
Above-mentioned three kinds of reagent charging capacity: CsNO 33.898 grams (0.02mol), ZnO 3.256 grams of (0.04mol), B 2o 32.089 grams (0.03mol).
Concrete operation step is: by above-mentioned dosage, take respectively reagent, they are put into mortar, mix and grind evenly, then pack in the corundum ceramic crucible of 10mL, by its compacting, put into retort furnace, with the speed of 100 ℃/h, be warming up to 500 ℃ and constant temperature 24h.Be down to and take out sample after room temperature and again grind evenly, then be placed in crucible and compacting, the speed with 150 ℃/h in retort furnace is warmed up to 800 ℃ of sintering 120h, takes out and grinds 2 times midway, obtains the CsZn of pure phase 2b 3o 7compound.
Embodiment 6
Adopt flux method, with Cs 2o-ZnF 2-B 2o 3fusing assistant system growth CsZn 2b 3o 7crystal.
Take 162.9 grams of (0.50mol) Cs 2cO 3, 32.6 grams of (0.40mol) ZnO, 62.0 grams of (0.60 mol) ZnF 2with 74.2 grams of (1.20mol) H 3bO 3, after mixed grinding is even, pack in batches
Figure BDA0000398740680000081
Figure BDA0000398740680000082
opening platinum crucible in.In retort furnace, with the speed of 100 ℃/h, be warming up to 700 ℃ and constant temperature 2 days, then cool to room temperature with the furnace.Take out sintering after product and add 74.2 grams of (1.20mol) H 3bO 3, after grinding evenly, put into
Figure BDA0000398740680000083
opening platinum crucible, in vertical crystal growing furnace, be warming up to 1000 ℃ fusing and constant temperature 10h so that melt homogenization.Speed with 4 ℃/h is cooled to 800 ℃, CsZn 2b 3o 7crystal is separated out at bath surface, then is cooled to room temperature with the speed of 50 ℃/h.Pick out transparent bulk crystals and it is carried out to powder x-ray diffraction analysis, confirm that gained crystal is CsZn 2b 3o 7crystal.
Cut gained crystal mass compared with good part as seed crystal, again raw material heat up is melted, be then cooled fast to above 10 ℃ of temperature of saturation.Lentamente the seed rod that seed crystal is housed is stretched in the melt of crucible, and start the wheelwork of seed rod upper end, slewing rate is 25 revs/min.Constant temperature is after half an hour, and fast cooling, to temperature of saturation, is then lowered the temperature with the speed of 0.5 ℃/day.After crystal grows into desired size, promote seed rod, make crystal depart from liquid level, will crystal stay annealing in stove and be cooled to room temperature with the speed of 20 ℃/h, get final product to obtain the CsZn of centimetre-sized 2b 3o 7crystal.
Embodiment 7
Adopt flux method, with Cs 2o-ZnF 2-B 2o 3fusing assistant system growth CsZn 2b 3o 7crystal.
Take 97.7 grams of (0.30mol) Cs 2cO 3, 16.3 grams of (0.20mol) ZnO, 62.0 grams of (0.60mol) ZnF 2with 49.5 grams of (0.80mol) H 3bO 3, after mixed grinding is even, pack in batches opening platinum crucible in.In retort furnace, with the speed of 100 ℃/h, be warming up to 700 ℃ and constant temperature 1 day, then cool to room temperature with the furnace.Take out sintering after product and add 49.5 grams of (0.80mol) H 3bO 3, after grinding evenly, put into
Figure BDA0000398740680000085
opening platinum crucible, in vertical crystal growing furnace, be warming up to 1000 ℃ fusing and constant temperature 20h so that melt homogenization.Be cooled fast to above 10 ℃ of temperature of saturation.Lentamente the seed rod that seed crystal is housed is stretched in the melt of crucible, and start the wheelwork of seed rod upper end, slewing rate is 25 revs/min.Constant temperature is after half an hour, and fast cooling, to temperature of saturation, is then lowered the temperature with the speed of 0.5 ℃/day.After crystal grows into desired size, promote seed rod, make crystal depart from liquid level, will crystal stay annealing in stove and be cooled to room temperature with the speed of 20 ℃/h, get final product to obtain the CsZn of centimetre-sized 2b 3o 7crystal.
Embodiment 8
Adopt flux method, with Cs 2o-ZnF 2-B 2o 3fusing assistant system growth CsZn 2b 3o 7crystal.
Take 162.9 grams of (0.50mol) Cs 2cO 3, 19.9 grams of (0.20mol) Zn (OH) 2, 62.0 grams of (0.60mol) ZnF 2with 61.8 grams of (1.00mol) H 3bO 3, after mixed grinding is even, pack in batches
Figure BDA0000398740680000091
opening platinum crucible in.In retort furnace, with the speed of 150 ℃/h, be warming up to 700 ℃ and constant temperature 2 days, then cool to room temperature with the furnace.Take out sintering after product and add 61.8 grams of (1.00mol) H 3bO 3, after grinding evenly, put into
Figure BDA0000398740680000093
opening platinum crucible, in vertical crystal growing furnace, be warming up to 1000 ℃ fusing and constant temperature 20h so that melt homogenization.Be cooled fast to above 10 ℃ of temperature of saturation.Lentamente the seed rod that seed crystal is housed is stretched in the melt of crucible, and start the wheelwork of seed rod upper end, slewing rate is 25 revs/min.Constant temperature is after half an hour, and fast cooling, to temperature of saturation, is then lowered the temperature with the speed of 0.5 ℃/day.After crystal grows into desired size, promote seed rod, make crystal depart from liquid level, will crystal stay annealing in stove and be cooled to room temperature with the speed of 20 ℃/h, get final product to obtain the CsZn of centimetre-sized 2b 3o 7crystal.
Adopt above method all can obtain the CsZn that is of a size of centimetre-sized 2b 3o 7non-linear optic crystal; Use large size crucible, and extend vegetative period, can obtain the CsZn of corresponding large-size 2b 3o 7crystal.
Through single-crystal X-ray diffraction analysis, the CsZn that above-described embodiment 5-6 is prepared 2b 3o 7crystal, containing symmetry centre, does not belong to rhombic system Cmc2 1spacer, unit cell parameters is
Figure BDA0000398740680000094
Figure BDA0000398740680000095
z=12.Fig. 3 is this CsZn 2b 3o 7the structural representation of crystal.
Embodiment 9
By the CsZn of embodiment 6 gained 2b 3o 7non-linear optic crystal makes to see through spectrum test, and the uv-absorbing cut-off limit of this crystal is about 218nm, and sees through in 218-2500nm wavelength region; This crystal is not easily broken, is easy to cutting, polishing and preservation, and deliquescence not; By the CsZn of embodiment 5 gained 2b 3o 7non-linear optic crystal, is placed on the position that accompanying drawing 1 shown device label is 3, at room temperature, with adjusting QNd:YAG laser apparatus, make fundamental frequency light source, incident wavelength is the near infrared light of 1064nm, the green laser that output wavelength is 532nm, and laser intensity is approximately equivalent to KDP (KH 2pO 4) 1.5 times; By the Li of embodiment 5 gained 4sr (BO 3) 2non-linear optic crystal, is placed on the position that accompanying drawing 1 shown device label is 3, at room temperature, with the green (light) laser of 532nm wavelength, make fundamental frequency light source, incident wavelength is the green glow of 532nm, the Ultra-Violet Laser that output wavelength is 266nm, and laser intensity is approximately equivalent to 1/3 times of BBO.

Claims (8)

1. a chemical formula is CsZn 2b 3o 7compound.
2. a CsZn 2b 3o 7the preparation method of compound, it is characterized in that, the preparation of employing solid reaction process, described method comprises the steps: after evenly mixing with stoichiometric ratio containing Cs compound, containing Zn compound and boride alloy, to be not more than the speed of 150 ℃/h, be warmed up to 500 ℃ and more than presintering 24h, then cooling is taken out and is ground evenly, then to be not more than more than 200 ℃/h is warmed up to 800 ℃ of sintering 72h, take out to grind more than 1 time midway, get final product to obtain this compound of pure phase.
3. a CsZn 2b 3o 7non-linear optic crystal, its chemical formula is CsZn 2b 3o 7, this crystal, containing symmetry centre, does not belong to rhombic system Cmc2 1spacer, unit cell parameters is
Figure FDA0000398740670000011
Figure FDA0000398740670000012
z=12.
4. prepare CsZn for one kind 2b 3o 7the method of non-linear optic crystal, is characterized in that, adopts flux method growth CsZn 2b 3o 7non-linear optic crystal, described fusing assistant is Cs 2o-ZnF 2-B 2o 3fusing assistant system.
5. method according to claim 4, is characterized in that, described method comprises the steps: described containing Cs compound, containing Zn compound, ZnF 2with boride alloy with mol ratio Cs:Zn:ZnF 2: B=3-5:1-2:3:8-12 mixes and grinds evenly, puts into after platinum crucible is warming up to 700 ℃ of sintering 1-2 days and is down to room temperature.Add again with raw material in the heavy boride alloy such as boride alloy, mixed grinding melts after evenly in crucible, growing crystal in high-temperature fusant surface or melt.
6. according to the method for claim 2 or 4, be further characterized in that, the described Cs compound that contains is selected from cesium carbonate, cesium bicarbonate, cesium nitrate or cesium hydroxide; The described Zn compound that contains is selected from zinc oxide, zinc carbonate or zinc hydroxide; Describedly containing boride alloy described in B chemical combination, be selected from H 3bO 3or B 2o 3.
7. according to the method for claim 4, it is characterized in that, described method also comprises CsZn 2b 3o 7the aftertreatment of non-linear optic crystal: after crystal growth finishes, will crystal stay in growth furnace and anneal, be down to room temperature to be not more than the speed of 100 ℃/h (being preferably less than 50 ℃/h).
8.CsZn 2b 3o 7the purposes of non-linear optic crystal, is characterized in that, described application comprises as device for non-linear optical to be used, and preferably, prepared device for non-linear optical comprises at least a branch of incidence electromagnetic radiation by least one CsZn 2b 3o 7after non-linear optic crystal, produce the device that at least a branch of frequency is different from the output radiation of incidence electromagnetic radiation.
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CN110079858A (en) * 2019-05-20 2019-08-02 闽江学院 A kind of cesium sulfate magnesium nonlinear optical crystal and its preparation method and purposes
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CN105780119A (en) * 2014-12-22 2016-07-20 中国科学院新疆理化技术研究所 Lead-barium bromoborate compound, lead-barium bromoborate crystal, preparation method and applications thereof
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CN110079858A (en) * 2019-05-20 2019-08-02 闽江学院 A kind of cesium sulfate magnesium nonlinear optical crystal and its preparation method and purposes
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CN110468445A (en) * 2019-09-23 2019-11-19 中国科学院新疆理化技术研究所 Boric acid caesium barium nonlinear optical crystal and its preparation method and application
CN110468445B (en) * 2019-09-23 2021-03-09 中国科学院新疆理化技术研究所 Cesium barium borate nonlinear optical crystal and preparation method and application thereof

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