CN102071464B - Nonlinear optical crystal material Sr3Y3BiB4O15 and preparation method and application thereof - Google Patents

Nonlinear optical crystal material Sr3Y3BiB4O15 and preparation method and application thereof Download PDF

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CN102071464B
CN102071464B CN2011100241470A CN201110024147A CN102071464B CN 102071464 B CN102071464 B CN 102071464B CN 2011100241470 A CN2011100241470 A CN 2011100241470A CN 201110024147 A CN201110024147 A CN 201110024147A CN 102071464 B CN102071464 B CN 102071464B
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高建华
宋立美
万云
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Northwest University
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Abstract

The invention discloses a nonlinear optical crystal material Sr3Y3BiB4O15 and a preparation method and application thereof. The crystal material is bismuth yttrium strontium borate shown as the chemical formula of Sr3Y3BiB4O15, belongs to a hexagonal system, and has the space group of P63 and the unit cell parameters of a=10.6975(13)A and c=6.7222(12)A. A crystal structure comprises BO3 radicals which are arranged in accordant direction and a BiO3 radical with lone pair electrons which are arranged in accordant direction, so that nonlinear effect is 3 to 5 times that of KH2PO4. A crystal has moderate hardness, is free from being deliquesced or cleaved, and is easy to cut, polish and store. The crystal grows by a flux growth method. The preparation method comprises the following steps of: mixing bismuth yttrium strontium borate and a fluxing agent; heating the mixture to obtain solution; stirring; preserving heat; cooling until the temperature is 0.5 to 3 DEG C above a saturation point; adding crystal seeds; controlling an appropriate temperature lowering speed; when the crystal grows to a certain degree, extracting the crystal out of a liquid surface; and slowly lowering the temperature to room temperature so as to obtain Sr3Y3BiB4O15 monocrystal. The crystal can serve as a frequency doubling crystal in an optical parametric oscillator and a harmonic generator. Moreover, the crystal comprises a yttrium element, so that other rare earth ions can be doped so as to obtain a self-frequency-doubling laser crystal.

Description

Non-linear optical crystal material Sr 3Y 3BiB 4O 15
Technical field
The present invention relates to the optoelectronic functional materials field, be specifically related to a kind of non-linear optic crystal Sr 3Y 3BiB 4O 15And fusing assistant growing method and purposes, and rear-earth-doped Sr 3Y 3BiB 4O 15Crystal and fusing assistant growing method and purposes.
Background technology
In recent years,, be used widely at numerous areas such as optics, communication, medical science, military affairs along with the fast development of laser technology, all solid state laser particularly is little because of its volume, price is low, advantages of simple structure and simple people's attention extremely.All solid state laser generally all is to produce laser by laser diode-pumped laser crystals, can produce the laser of 1064nm like pump-coupling Nd:YAG.The pumping laser crystal generally can only produce infrared laser, and can not obtain short wavelength's laser, and the laser that will produce shorter wavelength just must carry out frequency multiplication, sum of fundamental frequencies, difference frequency etc. with non-linear optic crystal, such as using non-linear optic crystal KTiOPO 4(KTP) the 1064nm laser that Nd:YAG is produced carries out frequency multiplication, can obtain the green laser of 532nm; Use non-linear optic crystal LiB 3O 5(LBO) the 1064nm laser that Nd:YAG is produced carries out the violet laser that frequency multiplication, sum of fundamental frequencies can get 355nm.Short wavelength's laser is high because of its single photon energy, and wavelength is short, in fields such as information storage, precision sizing, precision instrument, biological medicine, military affairs irreplaceable effect is arranged.Except aforesaid method, also can directly obtain short wavelength laser by laser diode pump-coupling self-frequency doubling laser crystal.So-called self-frequency doubling laser crystal mixes rare earth ion exactly in non-linear optic crystal, like Nd:YAB, YAB is YAl 3(BO 3) 4Abbreviation, YAB itself is a kind of nonlinear optical material, when plant its mix the Nd ion after, just become self-frequency doubling laser crystal.All can mix rare earth ion in not all nonlinear optical material becomes self-frequency doubling laser crystal, just not all right such as above KTP that mentions and LBO.The non-linear optic crystal that only comprises the element similar with the rare earth ion atomic radius just might become self-frequency doubling laser crystal.Resemble and contain yttrium (Y) element among the YAB, itself belongs to REE, therefore has similar atomic radius and character with other REEs, therefore can be replaced by other REEs, so can become self-frequency doubling laser crystal.
At present, more famous non-linear optical crystal material mainly contains following several kinds: KTiOPO 4(KTP), LiB 3O 5(LBO), β-BaB 2O 4(BBO), CsB 3O 5(CBO), CsLiB 6O 10(CLBO), K 2Al 2B 2O 7(KABO), KBeBO 3F (KBBF) etc.This different materials more or less all has certain shortcoming, such as, although the KTP non-linear effect is bigger, damage threshold is lower, can not produce high power laser; Although LBO, BBO, CBO, CLBO and KABO damage threshold are big but non-linear effect is less, and BBO, CBO, CLBO can not use in high humidity environment; Though it is shorter that the KBBF ultraviolet sees through wavelength, but the laser of 177nm produced, but Be unit have severe toxicity, and human body and environment are made a big impact, and this crystal of growth of large size high quality is relatively more difficult.In addition, some borates of bismuth-containing (Bi) element have caused extensive concern in recent years, not only comprise BO because in these compound structures, produce the group of non-linear effect 3Group and comprise the lone-pair electron of Bi-O group, this makes this compounds have bigger non-linear effect, such as BiB 3O 6(BIBO) has d Eff( />)=3.2pm/V, than KTP (<2.7pmV) also want big, and BIBO also has bigger damage threshold.
As noted earlier, become self-frequency doubling laser crystal, at first this host crystal must have the non-linearity effect, and next has can be by the substituted similar atom of rare earth ion.At present, the material that can be used as self-frequency doubling laser crystal has YAl 3(BO 3) 4(YAB), YCa 4O (BO 3) 3(YCOB), Na 3La 9O 3(BO 3) 8(NLBO), CaLa 2B 10O 19(LCB).These several kinds of crystalline shortcomings mainly are that non-linear effect is less, and this makes that the lasing efficiency that obtains is lower.
Summary of the invention
Purpose of the object of the invention provides a kind of inorganic nonlinear optical crystal, and its chemical formula is: Sr 3Y 3BiB 4O 15, have the non-linear effect of 3-5 KDP doubly;
Another object of the present invention provides above-mentioned non-linear optic crystal Sr 3Y 3BiB 4O 15Flux growth method;
Another purpose of the present invention provides above-mentioned non-linear optic crystal Sr 3Y 3BiB 4O 15As frequency-doubling crystal, can convert the laser that laser apparatus produces to short wavelength laser;
Last purpose of the present invention provides rare earth ion doped Sr 3Y 3BiB 4O 15Crystal can be used as self-frequency doubling laser crystal, can directly produce short wavelength laser.
In order to realize above-mentioned task, the present invention takes following technical solution:
A kind of non-linear optic crystal is characterized in that, this crystal is a bismuth boracic acid yttrium strontium, and molecular formula is Sr 3Y 3BiB 4O 15, it belongs to hexagonal system, and molecular weight is 1021.81, and unit cell parameters does a=10.6975 (13), c=6.7222 (12), V=666.2 3This hardness of crystals is moderate, deliquescence not, and cleavage is not easy to cutting, polishing and preserves.Non-linear effect is about 3-5 times of KDP.
When a small amount of rare earth ion that mixes, like Nd 3+, Yb 3+, Er 3+Behind the plasma, because Y 3+Radius similar with them, so big variation does not take place the structure after mixing, atomic arrangement can not change, just cell parameter has slight variations.
The growth method of above-mentioned bismuth boracic acid yttrium strontium crystal is characterized in that, adopts flux growth method, and its step is following:
(1) will contain strontium compound, contain yttrium compound, bismuth-containing compound and boron-containing compound and take by weighing by stoichiometric ratio after, grind, mix, put into retort furnace; 500 ℃ of sintering 4 hours, take out the cooling back and grind fully, put into retort furnace again, temperature is raised to 800 ℃ of sintering 10 hours; Take out the cooling back and grind fully, put into retort furnace again, temperature is raised to 900 ℃ of sintering 24 hours, takes out the cooling back and grinds fully; Put into retort furnace again, reburn at 900 ℃ and tied 24 hours, get Sr 3Y 3BiB 4O 15The polycrystal powder sample.
(2) with a small amount of Sr of gained in the step (1) 3Y 3BiB 4O 15Polycrystal powder sample and respective amount fusing assistant mix, and the little platinum crucible of Sheng Yuyi is raised to 850-950 ℃ with temperature, makes sample become melt, constant temperature 10 hours; The gained melt is slowly dropped to 600 ℃ with 5 ℃/hour, turn off stove again, from platinum crucible, separate obtaining Sr in the crystal of spontaneous crystallization 3Y 3BiB 4O 15Seed crystal;
(3) with a large amount of Sr of gained in the step (1) 3Y 3BiB 4O 15Polycrystal powder sample and respective amount fusing assistant mix, and the big platinum crucible of Sheng Yuyi is raised to 850-950 ℃ with temperature, makes sample become melt, stir after 5 hours constant temperature 10 hours with whisking appliance; Then the temperature of melt is slowly reduced on the temperature of saturation 0.5-3 ℃, then with the fixing Sr preferably of platinum filament 3Y 3BiB 4O 15Seed crystal is lowered to melt to seed crystal, makes seed crystal elder generation melt back a bit; Drop to saturation point then, slowly lower the temperature with the rate of temperature fall in (0.1 ℃-3 ℃)/sky again, lift from liquid level when treating crystal length to certain size; With (5 ℃-30 ℃)/hour rate of temperature fall drop to room temperature, can obtain Sr 3Y 3BiB 4O 15Non-linear optic crystal.
(4) rare earth ion doped Sr 3Y 3BiB 4O 15The growth method of self-frequency doubling laser crystal and Sr 3Y 3BiB 4O 15The growth method of non-linear optic crystal is identical, and difference only is in raw material, to add a certain amount of REE by stoichiometric ratio.The same step of other step (2), (3).
The polycrystal powder sample is prepared by the reactions formula described in the step (1):
6SrO+3Y 2O 3+Bi 2O 3+4B 2O 3→2Sr 3Y 3BiB 4O 15
In the formula, SrO can use SrCO 3, Sr (NO 3) 2, SrC 2O 4, CH 3COOSr, Sr (OH) 2Substitute; Y 2O 3Available Y (NO 3) 3, Y (CH 3COO) 3And it is alternative by C, N, O and Y coordinate title complex; Bi 2O 3Available Bi (NO 3) 3Or it is alternative by C, N, O and Bi coordinate title complex; B 2O 3Available H 3BO 3Substitute.
Said rare earth ion doped Sr 3Y 3BiB 4O 15The polycrystal powder sample is prepared by the reactions formula:
6SrO+3(1- x)Y 2O 3+? xRE 2O 3+Bi 2O 3+4B 2O 3→2Sr 3Y （3-3 x） RE 3 x BiB 4O 15；
In the formula, RE is for being Nd, Yb, Er, Ho, Tm 3One of;
SrO uses SrCO 3, Sr (NO 3) 2, SrC 2O 4, CH 3COOSr, Sr (OH) 2Substitute; Y 2O 3With Y (NO 3) 3, Y (CH 3COO) 3Or it is alternative by C, N, O and Y coordinate title complex; Bi 2O 3With Bi (NO 3) 3Or it is alternative by C, N, O and Bi coordinate title complex; B 2O 3Use H 3BO 3Substitute.
Above-mentioned surrogate produces CO in heat-processed 2, NO 2, H 2O, and overflow, thereby only generate the required composition of invention, and do not bring impurity component into.
Fusing assistant in the step (2) is preferably: M-Bi-B-F-O (M=Na, Li, Sr) system.Sr 3Y 3BiB 4O 15With the mol ratio of fusing assistant be 1:2.0 ~ 6.0.
(Sr) fusing assistant is to choose Li in molar ratio to said M-Bi-B-F-O for M=Na, Li 2CO 3, Na 2CO 3, SrCO 3, Bi 2O 3, H 3BO 3, SrF 2, NaF, NH 4F, 2 ~ 6 kinds of preparations among the LiF.
Sr 3Y 3BiB 4O 15Not only contain in the compound and arrange consistent BO 3Group, and contain the BiO that lone-pair electron are arranged unanimity 3Therefore group has bigger non-linear effect, and also comprises yttrium (Y) element in this crystal, and it can be by other REEs, like Nd 3+, Yb 3+, Er 3+Plasma replaces, and forms self-frequency doubling laser crystal.Because SYBB has bigger non-linear effect, the self-frequency doubling laser crystal that therefore forms can produce the laser of higher-wattage.Owing to adopt the laser structure of self-frequency doubling laser crystal simpler, so the cost of laser apparatus reduces greatly.
The compound S r that the present invention relates to 3Y 3BiB 4O 15(SYBB), be the brand-new material that the applicant prepares first, not at the Compound C d of bibliographical information 3Al 3BiB 4O 15(CABB) in the promoted extension of deriving of (referring to Journal of Solid State Chemistry 183 (2010) 2910 – 2916), because the two has tangible difference at aspects such as structure, character.
SYBB belongs to P6 3Spacer, cell parameter does a=10.6975 (13), c=6.7222 (12), V=666.2 3The CABB spacer is with also belonging to P6 3, but cell parameter does a=10.3919 (15), c=5.7215 (11), V=535.09 3
Bi and Sr occupy an independent position fully in the SYBB structure, and Y element and 7 oxygen form YO 7Polyhedron; And in CABB, Bi and Cd account for a position jointly, are in disturbance state, and Al element and 6 oxygen formation AlO 6Octahedra; So cause them both character have bigger difference just because of the arrangement of atom in the structure is different.SYBB has bigger non-linear effect, and CABB has less non-linear effect.And contain among the SYBB can be by the substituted yttrium of rare earth ion (Y) element, and does not have among the CABB.
The purposes of bismuth boracic acid yttrium strontium non-linear optic crystal of the present invention is: make frequency-doubling crystal at harmonic generator, optical parametric oscillator, conversion optical maser wavelength produces the laser of visible light to ultraviolet band.
The purposes of rare earth ion doped bismuth boracic acid yttrium strontium crystal provided by the invention is as self-frequency doubling laser crystal, in all solid state laser, as working-laser material, can directly produce short wavelength laser.
Advantage of the present invention is:
Bismuth boracic acid yttrium strontium crystal has bigger non-linear effect, and hardness of crystals is moderate, deliquescence not, and cleavage is not easy to processing, and chemical property is stable, and is high temperature resistant, just decomposition about 1000 ℃.And containing yttrium in the crystal, other REEs that can mix form self-frequency doubling laser crystal.Because matrix has big non-linear effect, so this self-frequency doubling laser crystal can be made compact construction, volume is little, power is bigger laser apparatus.
Description of drawings
Fig. 1 is Sr 3Y 3BiB 4O 15Powder x x ray diffration pattern x (Cu target).
Fig. 2 is Sr 3Y 3BiB 4O 15Crystalline structure figure.
Fig. 3 is that non-linear optic crystal is made the frequency doubling device synoptic diagram in the harmonic generator.Label among the figure is represented respectively: 1, half-wave plate; 2, set of lenses; 3, frequency-doubling crystal; 4, dispersing prism.
Fig. 4 is that non-linear optic crystal is used as the frequency doubling device synoptic diagram in the optical parametric oscillator.Label among the figure is represented respectively: 1, half-wave plate; 2, set of lenses; 3, resonator cavity; 4, frequency-doubling crystal; 5, resonator cavity; 6, dispersing prism.
Fig. 5 is that self-frequency doubling laser crystal is used for laser diode-pumped laser structure synoptic diagram.Label is represented respectively among the figure: 1, LD pumping source; 2, condenser lens; 3, self-frequency doubling laser crystal; 4, outgoing mirror; 5, output short wavelength laser.
Below in conjunction with accompanying drawing and embodiment the present invention is done further detailed description.
Embodiment
Below be the embodiment that the contriver provides, these embodiment are in order further to understand the present invention, to the invention is not restricted to these embodiment.
Following examples 1-2 is a SYBB powder solid phase synthesis, Sr 3Y 3BiB 4O 15Powder x x ray diffration pattern x (Cu target) as shown in Figure 1.
Embodiment 1:
Be SrCO in molar ratio 3: Y 2O 3: Bi 2O 3: H 3BO 3=6:3:1:8 takes by weighing following reagent:
SrCO 3: 8.8578 grams, Y 2O 3: 6.7743 grams, Bi 2O 3: 4.6596 grams, H 3BO 3: 4.9464 grams.
With claim reagent, in agate grinds, grind evenly, be transferred to then in the Pt crucible, put into retort furnace; 500 ℃ of sintering 4 hours, take out the cooling back and grind fully, put into retort furnace again, temperature is raised to 800 ℃ of sintering 10 hours; Take out the cooling back and grind fully, put into retort furnace again, temperature is raised to 900 ℃ of sintering 24 hours, takes out the cooling back and grinds fully; Put into retort furnace again, reburn at 900 ℃ and tied 24 hours, get Sr 3Y 3BiB 4O 15The polycrystal powder sample.
Embodiment 2:
Be SrCO in molar ratio 3: Y 2O 3: Bi 2O 3: H 3BO 3=6:3:1:8 takes by weighing following reagent:
SrCO 3: 2.2145 grams, Y 2O 3: 1.6936 grams, Bi 2O 3: 1.1649 grams, H 3BO 3: 1.237 grams.
With claim reagent place clean beaker, add the nitric acid liquation of a certain amount of 1mol/L, heated and stirred on magnetic stirring apparatus; The melt into clear solution adds a certain amount of Hydrocerol A, after waiting to be dissolved into clear solution; On electric furnace, slowly heat, gradually evaporating water.Be transferred to the solids component in the beaker in the Pt crucible then, place retort furnace to make it to burn, then 900 ℃ of sintering 24 hours at 800 ℃.Can get high-purity Sr 3Y 3BiB 4O 15The polycrystal powder sample.
Following examples 3-7 is RE:SYBB (RE=Nd, Yb, Er, Ho, Tm) powder solid phase synthesis, Sr 3Y 3BiB 4O 15Powder x x ray diffration pattern x (Cu target) as shown in Figure 1.
Embodiment 3:
Be SrCO in molar ratio 3: Y 2O 3: Nd 2O 3: Bi 2O 3: H 3BO 3=6:3: (1- x): x: 8 (0< x<0.5) take by weighing following reagent:
SrCO 3: 2.2145 grams, Y 2O 3: 1.5807 grams, Nd 2O 3: 0.1683 gram ( x=0.0005mol), Bi 2O 3: 1.1649 grams, H 3BO 3: 1.237 grams.
With claim reagent, in agate grinds, grind evenly, be transferred to then in the Pt crucible, put into retort furnace; 500 ℃ of sintering 4 hours, take out the cooling back and grind fully, put into retort furnace again, temperature is raised to 800 ℃ of sintering 10 hours; Take out the cooling back and grind fully, put into retort furnace again, temperature is raised to 900 ℃ of sintering 24 hours, takes out the cooling back and grinds fully; Put into retort furnace again, reburn at 900 ℃ and tied 24 hours, get Nd 3+: Sr 3Y 3BiB 4O 15The polycrystal powder sample.
Embodiment 4:
Be SrCO in molar ratio 3: Y 2O 3: Yb 2O 3: Bi 2O 3: H 3BO 3=6:3: (1- x): x: 8 (0< x<0.5) take by weighing following reagent:
SrCO 3: 2.2145 grams, Y 2O 3: 1.5807 grams, Yb 2O 3: 0.1970 gram ( x=0.0005mol), Bi 2O 3: 1.1649 grams, H 3BO 3: 1.237 grams.
With claim reagent, in agate grinds, grind evenly, be transferred to then in the Pt crucible, put into retort furnace; 500 ℃ of sintering 4 hours, take out the cooling back and grind fully, put into retort furnace again, temperature is raised to 800 ℃ of sintering 10 hours; Take out the cooling back and grind fully, put into retort furnace again, temperature is raised to 900 ℃ of sintering 24 hours, takes out the cooling back and grinds fully; Put into retort furnace again, reburn at 900 ℃ and tied 24 hours, get Yb 3+: Sr 3Y 3BiB 4O 15The polycrystal powder sample.
Embodiment 5:
Be SrCO in molar ratio 3: Y 2O 3: Er 2O 3: Bi 2O 3: H 3BO 3=6:3: (1- x): x: 8 (0< x<0.5) take by weighing following reagent:
SrCO 3: 2.2145 grams, Y 2O 3: 1.5807 grams, Er 2O 3: 0.1913 gram ( x=0.0005mol), Bi 2O 3: 1.1649 grams, H 3BO 3: 1.237 grams.
With claim reagent, in agate grinds, grind evenly, be transferred to then in the Pt crucible, put into retort furnace; 500 ℃ of sintering 4 hours, take out the cooling back and grind fully, put into retort furnace again, temperature is raised to 800 ℃ of sintering 10 hours; Take out the cooling back and grind fully, put into retort furnace again, temperature is raised to 900 ℃ of sintering 24 hours, takes out the cooling back and grinds fully; Put into retort furnace again, reburn at 900 ℃ and tied 24 hours, get Er 3+: Sr 3Y 3BiB 4O 15The polycrystal powder sample.
Embodiment 6:
Be SrCO in molar ratio 3: Y 2O 3: Ho 2O 3: Bi 2O 3: H 3BO 3=6:3: (1- x): x: 8 (0< x<0.5) take by weighing following reagent:
SrCO 3: 2.2145 grams, Y 2O 3: 1.5807 grams, Ho 2O 3:0.1889 gram ( x=0.0005mol), Bi 2O 3: 1.1649 grams, H 3BO 3: 1.237 grams.
With claim reagent, in agate grinds, grind evenly, be transferred to then in the Pt crucible, put into retort furnace; 500 ℃ of sintering 4 hours, take out the cooling back and grind fully, put into retort furnace again, temperature is raised to 800 ℃ of sintering 10 hours; Take out the cooling back and grind fully, put into retort furnace again, temperature is raised to 900 ℃ of sintering 24 hours, takes out the cooling back and grinds fully; Put into retort furnace again, reburn at 900 ℃ and tied 24 hours, get Ho 3+: Sr 3Y 3BiB 4O 15The polycrystal powder sample.
Embodiment 7:
Be SrCO in molar ratio 3: Y 2O 3: Tm 2O 3: Bi 2O 3: H 3BO 3=6:3: (1- x): x: 8 (0< x<0.5) take by weighing following reagent:
SrCO 3: 2.2145 grams, Y 2O 3: 1.5807 grams, Tm 2O 3: 0.1929 gram ( x=0.0005mol), Bi 2O 3: 1.1649 grams, H 3BO 3: 1.237 grams.
With claim reagent, in agate grinds, grind evenly, be transferred to then in the Pt crucible, put into retort furnace; 500 ℃ of sintering 4 hours, take out the cooling back and grind fully, put into retort furnace again, temperature is raised to 800 ℃ of sintering 10 hours; Take out the cooling back and grind fully, put into retort furnace again, temperature is raised to 900 ℃ of sintering 24 hours, takes out the cooling back and grinds fully; Put into retort furnace again, reburn at 900 ℃ and tied 24 hours, get Tm 3+: Sr 3Y 3BiB 4O 15The polycrystal powder sample.
Following examples 8-10 is the growth of SYBB crystalline, Sr wherein 3Y 3BiB 4O 15Seed crystal is to obtain Sr according to the preparing method's step (2) in the technical scheme 3Y 3BiB 4O 15Crystalline structure figure as shown in Figure 2.
Embodiment 8:
Be SYBB:Bi in molar ratio 2O 3: H 3BO 3: SrF 2=1: (2 ~ 6): (4 ~ 8): (1 ~ 3) takes by weighing reagent, evenly places the Pt crucible to the reagent mix that takes by weighing, and is fusion in 950 ℃ the retort furnace in temperature then; Put into crystal growing furnace after cooling; Temperature is raised to 950 ℃, makes sample become melt, stirs after 5 hours constant temperature 10 hours; Then melt temperature is slowly reduced on the temperature of saturation 0.5-3 ℃, then with a Sr preferably 3Y 3BiB 4O 15Seed crystal is fixed on the platinum filament, is lowered to melt, makes Sr 3Y 3BiB 4O 15Seed crystal elder generation melt back a bit drops to saturation point then, again with (0.1 ℃-3 ℃)/day rate of temperature fall slowly lower the temperature, treat the long liquid level of lifting from during to certain size of crystal, with (5 ℃-30 ℃)/hour rate of temperature fall drop to room temperature, can obtain Sr 3Y 3BiB 4O 15Non-linear optic crystal.
Embodiment 9:
Be SYBB:Bi in molar ratio 2O 3: H 3BO 3: NaF=1: (2 ~ 6): (2 ~ 5): (1 ~ 3) takes by weighing reagent, evenly places the Pt crucible to the reagent mix that takes by weighing, and is fusion in 950 ℃ the retort furnace in temperature then; Put into crystal growing furnace after cooling; Temperature is raised to 900 ℃, makes sample become melt, stirs after 5 hours constant temperature 10 hours; Then melt temperature is slowly reduced on the temperature of saturation 0.5-3 ℃, then with a Sr preferably 3Y 3BiB 4O 15Seed crystal is fixed on the platinum filament, is lowered to melt, makes Sr 3Y 3BiB 4O 15Seed crystal elder generation melt back a bit drops to saturation point then, again with (0.1 ℃-3 ℃)/day rate of temperature fall slowly lower the temperature, treat the long liquid level of lifting from during to certain size of crystal, with (5 ℃-30 ℃)/hour rate of temperature fall drop to room temperature, can obtain Sr 3Y 3BiB 4O 15Non-linear optic crystal.
Embodiment 10:
Be SYBB:Bi in molar ratio 2O 3: H 3BO 3: LiF=1: (2 ~ 6): (2 ~ 5): (1 ~ 3) takes by weighing reagent, evenly places the Pt crucible to the reagent mix that takes by weighing, and is fusion in 950 ℃ the retort furnace in temperature then; Put into crystal growing furnace after cooling; Temperature is raised to 880 ℃, makes sample become melt, stirs after 5 hours constant temperature 10 hours; Then melt temperature is slowly reduced on the temperature of saturation 0.5-3 ℃, then with a Sr preferably 3Y 3BiB 4O 15Seed crystal is fixed on the platinum filament, is lowered to melt, makes Sr 3Y 3BiB 4O 15Seed crystal elder generation melt back a bit drops to saturation point then, again with (0.1 ℃-3 ℃)/day rate of temperature fall slowly lower the temperature, treat the long liquid level of lifting from during to certain size of crystal, with (5 ℃-30 ℃)/hour rate of temperature fall drop to room temperature, can obtain Sr 3Y 3BiB 4O 15Non-linear optic crystal.
Following examples 11-15 is RE:SYBB (RE=Nd, Yb, Er, Ho, Tm) crystalline growth, Sr wherein 3Y 3BiB 4O 15Seed crystal is to obtain Sr according to the preparing method's step (2) in the technical scheme 3Y 3BiB 4O 15Crystalline structure figure as shown in Figure 2.
Embodiment 11:
Adopt instance 9 growth Sr 3Y 3BiB 4O 15The crystalline method is come growth of Nd 3+: the SYBB laser crystals.
Be (Nd in molar ratio 3+: SYBB): Bi 2O 3: H 3BO 3: NaF=1: (2 ~ 6): (2 ~ 5): (1 ~ 3) takes by weighing reagent, evenly places the Pt crucible to the reagent mix that takes by weighing, and is fusion in 950 ℃ the retort furnace in temperature then; Put into crystal growing furnace after cooling; Temperature is raised to 900 ℃, makes sample become melt, stirs after 5 hours constant temperature 10 hours; Then melt temperature is slowly reduced on the temperature of saturation 0.5-3 ℃, then with a Sr preferably 3Y 3BiB 4O 15Seed crystal is fixed on the platinum filament, is lowered to melt, makes Sr 3Y 3BiB 4O 15Seed crystal elder generation melt back a bit drops to saturation point then, again with (0.1 ℃-3)/day rate of temperature fall slowly lower the temperature, treat the long liquid level of lifting from during to certain size of crystal, with (5 ℃-30 ℃)/hour rate of temperature fall drop to room temperature, can obtain Nd 3+: Sr 3Y 3BiB 4O 15Self-frequency doubling laser crystal.
Embodiment 12:
Adopt instance 9 growth Sr 3Y 3BiB 4O 15The crystalline method Yb that grows 3+: the SYBB laser crystals.
Be (Yb in molar ratio 3+: SYBB): Bi 2O 3: H 3BO 3: NaF=1: (2 ~ 6): (2 ~ 5): (1 ~ 3) takes by weighing reagent, evenly places the Pt crucible to the reagent mix that takes by weighing, and is fusion in 950 ℃ the retort furnace in temperature then; Put into crystal growing furnace after cooling; Temperature is raised to 900 ℃, makes sample become melt, stirs after 5 hours constant temperature 10 hours; Then melt temperature is slowly reduced on the temperature of saturation 0.5-3 ℃, then with a Sr preferably 3Y 3BiB 4O 15Seed crystal is fixed on the platinum filament, is lowered to melt, makes Sr 3Y 3BiB 4O 15Seed crystal elder generation melt back a bit drops to saturation point then, again with (0.1 ℃-3 ℃)/day rate of temperature fall slowly lower the temperature, treat the long liquid level of lifting from during to certain size of crystal, with (5 ℃-30 ℃)/hour rate of temperature fall drop to room temperature, can obtain Yb 3+: Sr 3Y 3BiB 4O 15Self-frequency doubling laser crystal.
Embodiment 13:
Adopt instance 9 growth Sr 3Y 3BiB 4O 15The crystalline method Er that grows 3+: the SYBB laser crystals.
Be (Er in molar ratio 3+: SYBB): Bi 2O 3: H 3BO 3: NaF=1: (2 ~ 6): (2 ~ 5): (1 ~ 3) takes by weighing reagent, evenly places the Pt crucible to the reagent mix that takes by weighing, and is fusion in 950 ℃ the retort furnace in temperature then; Put into crystal growing furnace after cooling; Temperature is raised to 900 ℃, makes sample become melt, stirs after 5 hours constant temperature 10 hours; Then melt temperature is slowly reduced on the temperature of saturation 0.5-3 ℃, then with a Sr preferably 3Y 3BiB 4O 15Seed crystal is fixed on the platinum filament, is lowered to melt, makes Sr 3Y 3BiB 4O 15Seed crystal elder generation melt back a bit, again with (0.1 ℃-3 ℃)/day rate of temperature fall slowly lower the temperature, treat the long liquid level of lifting from during to certain size of crystal, with (5 ℃-30 ℃)/hour rate of temperature fall drop to room temperature, can obtain Er 3+: Sr 3Y 3BiB 4O 15Self-frequency doubling laser crystal.
Embodiment 14:
Adopt instance 9 growth Sr 3Y 3BiB 4O 15The crystalline method Ho that grows 3+: the SYBB laser crystals.
Be (Ho in molar ratio 3+: SYBB): Bi 2O 3: H 3BO 3: NaF=1: (2 ~ 6): (2 ~ 5): (1 ~ 3) takes by weighing reagent, evenly places the Pt crucible to the reagent mix that takes by weighing, and is fusion in 950 ℃ the retort furnace in temperature then; Put into crystal growing furnace after cooling; Temperature is raised to 900 ℃, makes sample become melt, stirs after 5 hours constant temperature 10 hours; Then melt temperature is slowly reduced on the temperature of saturation 0.5-3 ℃, then with a Sr preferably 3Y 3BiB 4O 15Seed crystal is fixed on the platinum filament, is lowered to melt, makes Sr 3Y 3BiB 4O 15Seed crystal elder generation melt back a bit drops to saturation point then, again with (0.1 ℃-3 ℃)/day rate of temperature fall slowly lower the temperature, treat the long liquid level of lifting from during to certain size of crystal, with (5 ℃-30 ℃)/hour rate of temperature fall drop to room temperature, can obtain Ho 3+: Sr 3Y 3BiB 4O 15Self-frequency doubling laser crystal.
Embodiment 15:
Adopt instance 9 growth Sr 3Y 3BiB 4O 15The crystalline method Tm that grows 3+: the SYBB laser crystals.
Be (Tm in molar ratio 3+: SYBB): Bi 2O 3: H 3BO 3: NaF=1: (2 ~ 6): (2 ~ 5): (1 ~ 3) takes by weighing reagent, evenly places the Pt crucible to the reagent mix that takes by weighing, and is fusion in 950 ℃ the retort furnace in temperature then; Put into crystal growing furnace after cooling; Temperature is raised to 900 ℃, makes sample become melt, stirs after 5 hours constant temperature 10 hours; Then melt temperature is slowly reduced on the temperature of saturation 0.5-3 ℃, then with a Sr preferably 3Y 3BiB 4O 15Seed crystal is fixed on the platinum filament, is lowered to melt, makes Sr 3Y 3BiB 4O 15Seed crystal elder generation melt back a bit drops to saturation point then, again with (0.1 ℃-3 ℃)/day rate of temperature fall slowly lower the temperature, treat the long liquid level of lifting from during to certain size of crystal, with (5 ℃-30 ℃)/hour rate of temperature fall drop to room temperature, can obtain Tm 3+: Sr 3Y 3BiB 4O 15Self-frequency doubling laser crystal.
The application that following examples 16,17 are used to prepare the frequency-doubling crystal device for the SYBB crystal.
Embodiment 16:
SYBB crystal of the present invention is used for the application of the frequency-doubling crystal device of harmonic emission device.
The SYBB crystal that above-mentioned arbitrary embodiment is obtained is installed in the position of label 3 among Fig. 3; Then frequency is that the fundamental frequency light of ω is behind slide 1 adjustment polarization direction; By through set of lenses 2 boundlings, incident and through frequency-doubling crystal 3 then, then a part of fundamental frequency phototransformation is that frequency is the frequency doubled light of 2 ω; Make the beam separation of different frequency again by dispersing prism, promptly get monochromatic frequency doubled light.
Embodiment 17:
SYBB crystal of the present invention is used for the brilliant application with the body device of frequency multiplication of parametric oscillator.
The SYBB crystal that above-mentioned arbitrary embodiment is obtained is installed in the position of label 4 among Fig. 4; Then frequency is that the fundamental frequency light of ω is behind slide 1 adjustment polarization direction; By through set of lenses 2 boundlings; Incide then in the resonator cavity 3,5, repeated oscillation is through frequency-doubling crystal 4, and then a part of fundamental frequency phototransformation is that frequency is ω 1+ ω 2And ω 1-ω 2Light, make the beam separation of different frequency again by dispersing prism, respectively frequency be ω 1+ ω 2And ω 1-ω 2Light.
Embodiment 18:
Rare earth ion doped SYBB crystal of the present invention is used for the application of the self-frequency doubling laser crystal of laser apparatus.
The rare earth ion doped SYBB crystal that the foregoing description 11 ~ 15 is obtained is installed in the position of label 3 among Fig. 5; Light by the generation of LD pumping source; After condensor converges, get into the self-frequency-doubling crystal, form resonator cavity, directly produce short wavelength laser with self-frequency-doubling crystal and outgoing mirror.

Claims (2)

1. the preparation method of a non-linear optic crystal, said crystal is rear-earth-doped bismuth boracic acid yttrium strontium, in all solid state laser as self-frequency doubling laser crystal, chemical formula Sr 3Y (3-3 x) RE 3 x BiB 4O 15, wherein 0< x<0.5 RE is rare earth ion Nd, Yb, Er, Ho, Tm one of them or more than one, belongs to hexagonal system, spacer P6 3, cell parameter is: a=10.6975 (13), c=6.7222 (12), it is characterized in that this method adopts flux growth method, its step is following:
(1) after the compound that will contain strontium compound, contains yttrium compound, bismuth-containing compound, boron-containing compound and contain said rare earth ion takes by weighing by stoichiometric ratio, grinds, mix; Put into retort furnace,, take out the cooling back and grind fully 500 ℃ of sintering 4 hours; Put into retort furnace again, temperature is raised to 800 ℃ of sintering 10 hours, takes out the cooling back and grinds fully; Put into retort furnace again, temperature is raised to 900 ℃ of sintering 24 hours, takes out the cooling back and grinds fully; Put into retort furnace again, reburn at 900 ℃ and tied 24 hours, get rear-earth-doped Sr 3Y 3BiB 4O 15The polycrystal powder sample;
(2) with the rear-earth-doped Sr of gained in the few steps (1) 3Y 3BiB 4O 15Polycrystal powder sample and respective amount fusing assistant mix, and the little platinum crucible of Sheng Yuyi is raised to 850-950 ℃ with temperature, makes sample become melt, constant temperature 10 hours; The gained melt is slowly dropped to 600 ℃ with 5 ℃/hour, turn off stove again, from platinum crucible, separate obtaining rear-earth-doped Sr in the crystal of spontaneous crystallization 3Y 3BiB 4O 15Seed crystal;
(3) with the rear-earth-doped Sr of gained in a large amount of steps (1) 3Y 3BiB 4O 15Polycrystal powder sample and respective amount fusing assistant mix, and the big platinum crucible of Sheng Yuyi is raised to 850-950 ℃ with temperature, makes sample become melt, stir after 5 hours constant temperature 10 hours with whisking appliance; Then the temperature of melt is slowly reduced on the temperature of saturation 0.5-3 ℃, then with the fixing said preferably rear-earth-doped Sr of platinum filament 3Y 3BiB 4O 15Seed crystal is lowered to melt to seed crystal, makes seed crystal elder generation melt back a bit; Drop to saturation point then, slowly lower the temperature with 0.1-3 ℃/day rate of temperature fall again, lift from liquid level when treating crystal length to certain size; Rate of temperature fall with 5-30 ℃/hour drops to room temperature, can obtain rear-earth-doped Sr 3Y 3BiB 4O 15Non-linear optic crystal.
2. the method for claim 1 is characterized in that, the said strontium compound that contains is SrCO 3, Sr (NO 3) 2, SrC 2O 4, CH 3COOSr or Sr (OH) 2, containing yttrium compound is Y (NO 3) 3Or Y (CH 3COO) 3, bismuth-containing compound is Bi (NO 3) 3, boron-containing compound is H 3BO 3
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