CN103590106B - The Preparation method and use of fluoroboric acid strontium non-linear optic crystal - Google Patents

The Preparation method and use of fluoroboric acid strontium non-linear optic crystal Download PDF

Info

Publication number
CN103590106B
CN103590106B CN201210293691.XA CN201210293691A CN103590106B CN 103590106 B CN103590106 B CN 103590106B CN 201210293691 A CN201210293691 A CN 201210293691A CN 103590106 B CN103590106 B CN 103590106B
Authority
CN
China
Prior art keywords
crystal
temperature
fluoroboric acid
acid strontium
seed
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Active
Application number
CN201210293691.XA
Other languages
Chinese (zh)
Other versions
CN103590106A (en
Inventor
潘世烈
黄振军
田雪林
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Xinjiang Technical Institute of Physics and Chemistry of CAS
Original Assignee
Xinjiang Technical Institute of Physics and Chemistry of CAS
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Xinjiang Technical Institute of Physics and Chemistry of CAS filed Critical Xinjiang Technical Institute of Physics and Chemistry of CAS
Priority to CN201210293691.XA priority Critical patent/CN103590106B/en
Publication of CN103590106A publication Critical patent/CN103590106A/en
Application granted granted Critical
Publication of CN103590106B publication Critical patent/CN103590106B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Abstract

The present invention relates to a kind of Preparation method and use of fluoroboric acid strontium non-linear optic crystal, adopt solid reaction process synthetic compound and flux method growing crystal, described method is simple to operate, and cost is low; Prepared crystal not deliquescence in atmosphere, good mechanical property, not easily broken, physico-chemical property is stablized, and easily processes, and is suitable for making device for non-linear optical.The fluoroboric acid strontium non-linear optic crystal frequency-doubled effect obtained by the method is about 3 times of KDP, can be used widely in the non-linear optic crystal such as frequency-doubled conversion, optical parametric oscillator device.

Description

The Preparation method and use of fluoroboric acid strontium non-linear optic crystal
Technical field
The present invention relates to a kind of Preparation method and use of non-linear optic crystal, particularly relate to a kind of Preparation Method And The Use of the fluoroboric acid strontium non-linear optic crystal containing halogen.
Background technology
Nearly ten years, due to deepening continuously of the social development based on communication and information, the non-linear optic crystal as one of important information material (comprising laser frequency material, photoelectric material and photorefractive material) being is developed rapidly.The research fields such as current nonlinear optical material crystal is widely used in laser frequency conversion, light beam turns to, image multiplication, optical information processing, optical storage, optical-fibre communications, underwater communication, laser countermeasure (s) and nucleosynthesis.Along with the development of laser technology, find and can be applied to the focus that the ultraviolet even laser frequency doubling crystal in deep ultraviolet region are scientific circles' research non-linear optic crystals always.
In constantly studying and exploring, the compound of borate series receives much concern.In borate crystal molecule, can there is the BO of three-fold coordination configuration in B atom 3, the BO of four-coordination configuration can be there is again in group 4, chain, layer, three-D space structure can be interconnected to form; Simultaneously due to electronegativity and the O atom of B atom electronegativity comparatively greatly, therefore B-O key all can provide through UV-light and comparatively be widely studied, and has emerged large quantities of non-linear compound crystalline material with excellent frequency-doubled effect, as β-BaB 2o 4(BBO), LiB 3o 5(LBO), KBe 2bO 3f 2(KBBF) etc.The frequency-doubled conversion crystal of ultraviolet band, that study the earliest is KB5, although it can reach vacuum ultraviolet through wave band, Clock Multiplier Factor is very little.Find under study for action after borate combines with halogen atom, be conducive to the raising of nonlinear optical coefficients and the blue shift of ultraviolet absorption edge simultaneously.The comparatively deep halogenation borate of current research is as fluorine beryllium potassium borate KBe 2bO 3f 2, chloroboric acid potassium K 3b 6o 10cl, bromine potassium borate K 3b 6o 10br.
Through characterizing: number of patent application 201110258171.0 barium fluoborate Ba 3b 6o 11f 2crystal and fluoroboric acid strontium Sr of the present invention 3b 6o 11f 2crystal belongs to isomorphism crystal.In order to better test the Fundamental Physical Properties (comprising linear processes optical property) of this crystal, need the size of this crystal to reach several millimeters of even other monocrystalline of centimetre-sized, but not yet can obtain the fluoroboric acid strontium Sr that size is enough to for physical property measurement 3b 6o 11f 2the report of monocrystalline, more cannot commercially buy this crystal.Therefore the present invention adopts flux method to grow and obtains centimetre-sized fluoroboric acid strontium Sr 3b 6o 11f 2monocrystalline.
Summary of the invention:
The object of the invention is to provide a kind of fluoroboric acid strontium Sr 3b 6o 11f 2the preparation method of non-linear optic crystal;
Another object of the present invention is to provide a kind of fluoroboric acid strontium Sr obtained by the method 3b 6o 11f 2the purposes of non-linear optic crystal.
The preparation method of a kind of fluoroboric acid strontium non-linear optic crystal of the present invention, adopt flux method to prepare crystal, concrete operation step follows these steps to carry out:
A, mortar will be put into by chemical formula metering than taking containing strontium, fluorine-containing, boron-containing compound, mixing carefully grinding, loading corundum crucible, put into retort furnace, be slowly warming up to 300 DEG C, constant temperature 3 hours, be cooled to grinding at room temperature even, be slowly warming up to 450 DEG C, gas drained only, take out crucible after cooling, by sample grinding evenly, then be placed in crucible, retort furnace is warming up to 630 DEG C, after constant temperature 72-96 hour, sample is taken out, put into mortar and smash grinding to pieces, obtain fluoroboric acid strontium Sr 3b 6o 11f 2compound single-phase polycrystal powder, then X-ray analysis is carried out to this polycrystal powder;
B, by the fluoroboric acid strontium Sr in step a 3b 6o 11f 2compound single-phase polycrystal powder and fusing assistant PbO, H 3bO 3, LiF or NaF or KF mix, 890-940 DEG C is heated to the temperature rise rate of temperature 30-80 DEG C/h, constant temperature 20-30 hour, be cooled to 860-880 DEG C again, obtain mixing solutions, under temperature 840-860 DEG C of condition, seed rod is entered in melt fast, treat that it produces drift crystalline substance, constant temperature 0.5h floats crystalline substance and does not change, and then slowly drops to temperature 830 DEG C with the speed of temperature 0.5-2 DEG C/h, then seed rod is proposed liquid level, be down to room temperature with the speed of temperature 10-50 DEG C/h, fluoroboric acid strontium Sr can be obtained 3b 6o 11f 2seed crystal, wherein fluoroboric acid strontium Sr 3b 6o 11f 2with fusing assistant H 3bO 3, the mol ratio of PbO, LiF or NaF or KF is 1: 4: 1: 2-3;
C, prepare fluoroboric acid strontium Sr by step b again 3b 6o 11f 2with fusing assistant carry out mixture, load in the opening platinum crucible of Φ 80mm × 80mm, put into crystal growing furnace, 890-940 DEG C is heated to the temperature rise rate of temperature 30-80 DEG C/h, constant temperature 20-30 hour, then be cooled to temperature 880-860 DEG C, obtain the mixed molten liquid of fluoroboric acid strontium and fusing assistant;
D, the seed crystal obtained by step b are fixed on seed rod, seed crystal from crystal growing furnace top, first preheating seed crystal 5-60 minute, then 850-860 DEG C is cooled to, make seed crystal and step c blend melt surface contact or stretch in blend melt, with the rotating speed rotary seed crystal rod of 20-50rpm, with the speed slow cooling of temperature 1-3 DEG C/d to crystal growth to desired size;
E, arrive after required yardstick until single crystal growing, by crystal lift-off molten surface, be down to room temperature with the speed of temperature 20-50 DEG C/h, then crystal taken out from burner hearth, fluoroboric acid strontium Sr can be obtained 3b 6o 11f 2non-linear optic crystal.
Compound containing strontium described in step a is Sr 2cO 3, Sr (NO 3) 2, SrO, Sr (OH) 2, SrC 2o 4or SrSO 4; Fluorine-containing compound is SrF 2, HF; Boron-containing compound is H 3bO 3or B 2o 3.
The purposes of the fluoroboric acid strontium non-linear optic crystal that described method obtains, this crystal is used at preparation times frequency generator, upper frequency transmodulator, lower frequency transmodulator or optical parametric oscillator.
The preparation method of fluoroboric acid strontium non-linear optic crystal of the present invention, the chemical formula of this compound fluoroboric acid strontium non-linear optic crystal is Sr 3b 6o 11f 2, belong to oblique system, spacer P2 1, molecular weight is 541.72, and cell parameter is β=101.621 (1) °, non-linear optical effect is about 3 times of KDP, in atmosphere not deliquescence, and growth cycle is short, is easy to cutting, polishing and preservation, is suitable for making device for non-linear optical.
The electromagnetic radiation that upper or lower frequency transmodulator, times frequency generator or optical parametric oscillator comprise at least a branch of incidence as preparation is different from the device of the output radiation of incidence electromagnetic radiation by producing at least a branch of frequency after at least one block of non-linear optic crystal.
Described fluoroboric acid strontium compound can with fluoroboric acid strontium with equivalent containing B, containing Sr, mixture replacing containing F compound.
Fluoroboric acid strontium Sr of the present invention 3b 6o 11f 2non-linear optic crystal adopts general chemical synthesis process can prepare fluoroboric acid strontium polycrystal powder, again the polycrystal powder of preparation is mixed with fusing assistant (or adopting fluoroboric acid strontium starting raw material directly to mix in molar ratio), adopt flux method growth can obtain certain size fluoroboric acid strontium Sr 3b 6o 11f 2non-linear optic crystal, prepares the preferred solid phase synthesis method of polycrystal powder, that is: will containing Sr, B and F by metering than after mixing, heat and carry out solid state reaction, can obtain chemical formula is Sr 3b 6o 11f 2compound.When fluorine-containing compound is HF, operate under room temperature during reaction; When fusing assistant be PbO, LiF or NaF or KF time can reduce the melt temperature of system significantly.
Prepare fluoroboric acid strontium (Sr 3b 6o 11f 2) chemical equation of polycrystalline compounds:
(1)SrCO 3+SrF 2+H 3BO 3→Sr 3B 6O 11F 2+H 2O↑+CO 2↑
(2)Sr(NO 3) 2+SrF 2+B 2O 3→Sr 3B 6O 11F 2+NO 2↑+H 2O↑
(3)SrSO 4+SrF 2+H 3BO 3→Sr 3B 6O 11F 2+H 2O↑+SO 2
(4)SrO+SrF 2+B 2O 3→Sr 3B 6O 11F 2+H 2O↑
(5)Sr(OH) 2+SrF 2+H 3BO 3→Sr 3B 6O 11F 2+H 2O↑
(6)SrC 2O 4+SrF 2+B 2O 3→Sr 3B 6O 11F 2+H 2O↑+CO 2↑
(7)SrCO 3+HF+H 3BO 3→Sr 3B 6O 11F 2+H 2O↑+CO 2↑
(8)Sr(NO 3) 2+HF+B 2O 3→Sr 3B 6O 11F 2+NO 2↑+H 2O↑
(9)Sr(OH) 2+HF+H 3BO 3→Sr 3B 6O 11F 2+H 2O↑
(10)SrO+HF+B 2O 3→Sr 3B 6O 11F 2+H 2O↑
(11)SrC 2O 4+HF+H 3BO 3→Sr 3B 6O 11F 2+H 2O↑+CO 2↑
Commercially available reagent and raw material can be adopted containing strontium, fluorine-containing, boracic in the present invention.
Described fluoroboric acid strontium Sr 3b 6o 11f 2the preparation method of non-linear optic crystal, adopts compound flux method growing crystal.
Certain size fluoroboric acid strontium Sr prepared by the present invention 3b 6o 11f 2non-linear optic crystal, as preparing non-linear optic crystal device, comprises preparation times frequency generator, upper or lower frequency transmodulator and optical parameter oscillator.Described fluoroboric acid strontium Sr 3b 6o 11f 2non-linear optic crystal making nonlinear device comprises the coherent light by being different from incident light through at least a branch of frequency of at least a branch of incident fundamental wave generation.
Fluoroboric acid strontium Sr of the present invention 3b 6o 11f 2the preparation method of non-linear optic crystal, the compound fluoroboric acid strontium non-linear optic crystal structure obtained by the method is: F -ion, Sr 2+ion and [B 6o 14] group arrangement, form three-dimensional net structure.[B in this structure 6o 14] basic structure group is by 4 BO 4group and 2 BO 3every two BO of group composition 4tetrahedron and a BO 3trilateral is by Sharing Center O atom composition B 3o 8group, every two B 3o 8b is formed further by sharing two O atoms 6o 14group.B 6o 14group becomes tridimensional network by sharing dihedral, and Sr and F atom are filled in nine yuan of pore passage structures in this boron oxygen three-dimensional structure.
Accompanying drawing explanation
Fig. 1 is the powder x-ray diffraction collection of illustrative plates of fluoroboric acid strontium crystal of the present invention.
Fig. 2 is the basic framework figure of fluoroboric acid strontium crystal of the present invention, and wherein Sr is strontium, and B is boron, and O is oxygen, and F is fluorine.
Fig. 3 is the fundamental diagram of the device for non-linear optical that fluoroboric acid strontium crystal of the present invention makes, and wherein: 1 is laser apparatus, 2 is complete poly-mirror, and 3 for injecting crystal, and 4 is beam splitting prism, and 5 is filter plate.
Embodiment
Below in conjunction with drawings and Examples, the present invention is described in detail:
Embodiment 1:
For reaction formula (1), but be not limited to reaction formula (1)
SrCO 3+ SrF 2+ H 3bO 3→ Sr 3b 6o 11f 2+ H 2o ↑+CO 2↑ synthesis Sr 3b 6o 11f 2crystal, concrete operations are as follows:
By SrCO 3, SrF 2, H 3bO 3mortar is put into the ratio of 2: 1: 6, mix to take and put into mortar, mixing is also carefully ground, load corundum crucible, put into retort furnace, slowly be warming up to 300 DEG C, constant temperature 3 hours, is cooled to grinding at room temperature even, take out crucible after cooling, by sample grinding evenly, then be placed in crucible, retort furnace be warming up to 630 DEG C, sample took out after 72 hours by constant temperature, put into mortar to smash grinding to pieces and namely obtain fluoroboric acid strontium compound single-phase polycrystalline powder, then X-ray analysis is carried out to this polycrystal powder, gained X-ray spectrogram and finished product Sr 3b 6o 11f 2monocrystalline last X-ray spectrogram of pulverizing is consistent;
Growing large-size fluoroboric acid strontium Sr in blend melt 3b 6o 11f 2crystal:
By the compound fluoroboric acid strontium Sr of synthesis 3b 6o 11f 2polycrystal powder and fusing assistant Sr in molar ratio 3b 6o 11f 2: H 3bO 3: carry out mixture at PbO: LiF=1: 4: 1: 2, load in the opening platinum crucible of Φ 80mm × 80mm, put into crystal growing furnace, 930 DEG C are heated to the temperature rise rate of temperature 30 DEG C/h, constant temperature 24 hours, be cooled to temperature 860 DEG C again, obtain the mixed molten liquid of fluoroboric acid strontium and fusing assistant, enter seed rod in melt fast, treat that it produces drift crystalline substance, constant temperature 0.5h floats crystalline substance and does not change, then temperature 830 DEG C is slowly dropped to the speed of temperature 1 DEG C/h, seed rod is proposed liquid level, is down to room temperature with the speed of temperature 10 DEG C/h, fluoroboric acid strontium seed crystal can be obtained;
And then prepare the blend melt of fluoroboric acid strontium and fusing assistant, Sr in molar ratio 3b 6o 11f 2: H 3bO 3: carry out mixture at PbO: LiF=1: 4: 1: 2, loads in the opening platinum crucible of Φ 80mm × 80mm, put into crystal growing furnace, 930 DEG C are heated to the temperature rise rate of temperature 30 DEG C/h, constant temperature 30 hours, then be cooled to temperature 873 DEG C, obtain the mixed molten liquid of fluoroboric acid strontium and fusing assistant;
The seed crystal of acquisition is fixed on seed rod, seed crystal from crystal growing furnace top, first preheating seed crystal 5 minutes, then decline and make the blend melt surface contact of seed crystal and fluoroboric acid strontium and fusing assistant, be cooled to temperature 865 DEG C, with the rotating speed rotary seed crystal rod of 20rpm, with the speed slow cooling of temperature 1.5 DEG C/d to crystal desired size;
Arrive after required yardstick until single crystal growing, by crystal lift-off molten surface, be down to room temperature with the speed of temperature 50 C/h, then crystal is taken out from burner hearth, 23mm × 15mm × 11mm fluoroboric acid strontium can be obtained.
Embodiment 2:
For reaction formula (2), but be not limited to reaction formula (2)
Sr (NO 3) 2+ SrF 2+ B 2o 3→ Sr 3b 6o 11f 2+ NO 2↑+H 2o ↑ synthesis Sr 3b 6o 11f 2crystal, concrete operation step carries out according to embodiment 1;
By the compound fluoroboric acid strontium Sr of synthesis 3b 6o 11f 2polycrystal powder and fusing assistant H 3bO 3with NaF and PbO Sr in molar ratio 3b 6o 11f 2: H 3bO 3: load in the opening platinum crucible of Φ 80mm × 80mm at PbO: NaF=1: 4: 1: 3, put into crystal growing furnace, 940 DEG C are heated with the temperature rise rate of temperature 70 C/h, constant temperature 24 hours, be cooled to 880 DEG C again, obtain the mixed molten liquid of fluoroboric acid strontium and fusing assistant, seed rod is entered in melt fast, treat that it produces drift crystalline substance, constant temperature 0.5h floats crystalline substance and does not change, and then slowly drops to temperature 800 DEG C with the speed of temperature 0.8 DEG C/h, seed rod is proposed liquid level, be down to room temperature with the speed of temperature 10 DEG C/h, fluoroboric acid strontium seed crystal can be obtained;
And then prepare the blend melt of fluoroboric acid strontium and fusing assistant, Sr in molar ratio 3b 6o 11f 2: H 3bO 3: carry out mixture at PbO: NaF=1: 4: 1: 3, loads in the opening platinum crucible of Φ 80mm × 80mm, put into crystal growing furnace, temperature 940 DEG C is heated to the temperature rise rate of temperature 70 C/h, constant temperature 30 hours, then be cooled to temperature 885 DEG C, obtain the mixed molten liquid of fluoroboric acid strontium and fusing assistant;
The seed crystal of acquisition is fixed on seed rod, seed crystal from crystal growing furnace top, first preheating seed crystal 20 minutes, then 865 DEG C are cooled to, then decline and make the blend melt surface contact of seed crystal and fluoroboric acid strontium and fusing assistant, with the rotating speed rotary seed crystal rod of 20rpm or crucible, with the speed slow cooling of temperature 1 DEG C/d to crystal desired size;
Arrive after required yardstick until single crystal growing, by crystal lift-off molten surface, be down to room temperature with the speed of temperature 20 DEG C/h, then crystal taken out from burner hearth, 25mm × 18mm × 14mm fluoroboric acid strontium can be obtained.
Sr (NO in raw material 3) 2can by corresponding SrCO 3, SrO, Sr (OH) 2, SrSO 4or SrC 2o 4substitute; B 2o 3can by H 3bO 3corresponding alternative.
Embodiment 3:
For reaction formula (3), but be not limited to reaction formula (3)
By SrSO 4+ SrF 2+ H 3bO 3→ Sr 3b 6o 11f 2+ H 2o ↑+SO 2
Reaction formula synthetic compound Sr 3b 6o 11f 2, concrete operation step carries out according to embodiment 1;
By the compound fluoroboric acid strontium Sr of synthesis 3b 6o 11f 2single-phase polycrystalline powder and fusing assistant Sr in molar ratio 3b 6o 11f 2: H 3bO 3: carry out mixture at PbO: KF=1: 4: 1: 2, load in the opening platinum crucible of Φ 80mm × 80mm, put into crystal growing furnace, 900 DEG C are heated to the temperature rise rate of temperature 80 DEG C/h, constant temperature 20 hours, be cooled to 865 DEG C again, obtain the mixed molten liquid of fluoroboric acid strontium and fusing assistant, enter seed rod in melt fast, treat that it produces drift crystalline substance, constant temperature 0.5h floats crystalline substance and does not change, 810 DEG C are slowly dropped to the speed of temperature 1.5 DEG C/h, seed rod is proposed liquid level, is down to room temperature with the speed of temperature 10 DEG C/h, fluoroboric acid strontium seed crystal can be obtained;
And then prepare the blend melt of fluoroboric acid strontium and fusing assistant, Sr in molar ratio 3b 6o 11f 2: H 3bO 3: carry out mixture at PbO: KF=1: 4: 1: 2, loads in the opening platinum crucible of Φ 80mm × 80mm, put into crystal growing furnace, 900 DEG C are heated to the temperature rise rate of temperature 80 DEG C/h, constant temperature 20 hours, then be cooled to temperature 880 DEG C, obtain the mixed molten liquid of fluoroboric acid strontium and fusing assistant;
The seed crystal of acquisition is fixed on seed rod, seed crystal from crystal growing furnace top, first preheating seed crystal 10 minutes, then decline and make the blend melt surface contact of seed crystal and fluoroboric acid strontium and fusing assistant, be cooled to 870 DEG C, with the rotating speed rotary seed crystal rod of 40rpm, with the speed slow cooling of temperature 2.5 DEG C/d to crystal desired size;
Arrive after required yardstick until single crystal growing, by crystal lift-off molten surface, be down to room temperature with the speed of temperature 25 DEG C/h, then crystal taken out from burner hearth, 15mm × 12mm × 7mm fluoroboric acid strontium crystal can be obtained.
SrSO in raw material 4can by corresponding SrCO 3, SrO, Sr (OH) 2, Sr (NO 3) 2or SrC 2o 4substitute; H 3bO 3can by corresponding B 2o 3substitute.
Embodiment 4:
For reaction formula (4), but be not limited to reaction formula (4)
By SrO+SrF 2+ B 2o 3→ Sr 3b 6o 11f 2+ H 2o ↑, concrete operation step carries out according to embodiment 1;
By the fluoroboric acid strontium Sr of synthesis 3b 6o 11f 2compound single-phase polycrystal powder and fusing assistant Sr in molar ratio 3b 6o 11f 2: H 3bO 3: carry out mixture at PbO: KF=1: 4: 1: 2, load in the opening platinum crucible of Φ 80mm × 80mm, put into crystal growing furnace, 940 DEG C are heated to the temperature rise rate of temperature 80 DEG C/h, constant temperature 40 hours, be cooled to 880 DEG C again, obtain the mixed molten liquid of fluoroboric acid strontium and fusing assistant, seed rod is entered in melt fast, treat that it produces drift crystalline substance, constant temperature 0.5h floats crystalline substance and does not change, with the speed slow cooling to 820 DEG C of temperature 1 DEG C/h, seed rod is proposed liquid level, 640 DEG C are cooled to again with the speed of temperature 5 DEG C/h, room temperature is down to the speed of temperature 18 DEG C/h, fluoroboric acid strontium seed crystal can be obtained,
And then prepare the blend melt of fluoroboric acid strontium and fusing assistant, Sr in molar ratio 3b 6o 11f 2: H 3bO 3: carry out mixture at PbO: KF=1: 4: 1: 2, loads in the opening platinum crucible of Φ 80mm × 80mm, put into crystal growing furnace, 940 DEG C are heated to the temperature rise rate of temperature 80 DEG C/h, constant temperature 40 hours, then be cooled to temperature 880 DEG C, obtain the mixed molten liquid of fluoroboric acid strontium and fusing assistant;
The seed crystal of acquisition is fixed on seed rod, seed crystal from crystal growing furnace top, first preheating seed crystal 5 minutes, then stretch into as in blend melt, be cooled to temperature 875 DEG C, with the rotating speed rotary seed crystal rod of 50rpm, with the speed slow cooling of temperature 3 DEG C/d to crystal desired size;
Arrive after required yardstick until single crystal growing, by crystal lift-off molten surface, be down to room temperature with the speed of temperature 20 DEG C/h, crystal is taken out from burner hearth, 23mm × 19mm × 17mm fluoroboric acid strontium crystal can be obtained.
In raw material, SrO's can by corresponding SrCO 3, SrSO 4, Sr (OH) 2, Sr (NO 3) 2or SrC 2o 4substitute; B 2o 3can by H 3bO 3corresponding alternative
Embodiment 5:
For reaction formula (5), but be not limited to reaction formula (5)
By Sr (OH) 2+ SrF 2+ H 3bO 3→ Sr 3b 6o 11f 2+ H 2o ↑ synthetic compound Sr 3b 6o 11f 2, concrete operation step carries out according to embodiment 1;
By the compound fluoroboric acid strontium Sr of synthesis 3b 6o 11f 2single-phase polycrystalline powder and fusing assistant Sr in molar ratio 3b 6o 11f 2: H 3bO 3: carry out mixture at PbO: LiF=1: 4: 1: 2, load in the opening platinum crucible of Φ 80mm × 80mm, put into crystal growing furnace, 940 DEG C are heated to the temperature rise rate of temperature 70 C/h, constant temperature 30 hours, be cooled to 880 DEG C again, obtain the mixed molten liquid of fluoroboric acid strontium and fusing assistant, enter seed rod in melt fast, treat that it produces drift crystalline substance, constant temperature 0.5h floats crystalline substance and does not change, 830 DEG C are slowly dropped to the speed of temperature 2.5 DEG C/h, seed rod is proposed liquid level, is down to room temperature with the speed of temperature 20 DEG C/h, fluoroboric acid strontium seed crystal can be obtained;
And then prepare the blend melt of fluoroboric acid strontium and fusing assistant, Sr in molar ratio 3b 6o 11f 2: H 3bO 3: carry out mixture at PbO: LiF=1: 4: 1: 2, loads in the opening platinum crucible of Φ 80mm × 80mm, put into crystal growing furnace, 950 DEG C are heated to the temperature rise rate of temperature 70 C/h, constant temperature 24 hours, then be cooled to temperature 895 DEG C, obtain the mixed molten liquid of fluoroboric acid strontium and fusing assistant;
The seed crystal of acquisition is fixed on seed rod, seed crystal from crystal growing furnace top, first preheating seed crystal 25 minutes, then decline and make the blend melt surface contact of seed crystal and fluoroboric acid strontium and fusing assistant, be cooled to 878 DEG C, with the rotating speed rotary seed crystal rod of 30rpm, with the speed slow cooling of temperature 3 DEG C/d to crystal desired size;
Arrive after required yardstick until single crystal growing, by crystal lift-off molten surface, be down to room temperature with the speed of temperature 20 DEG C/h, then crystal taken out from burner hearth, 21mm × 17mm × 11mm fluoroboric acid strontium crystal can be obtained.
Sr (OH) in raw material 2can by corresponding SrCO 3, SrO, SrSO 4, SrSO 4, Sr (NO 3) 2or SrC 2o 4substitute; H 3bO 3can by corresponding B 2o 3substitute.
Embodiment 6:
For reaction formula (6), but be not limited to reaction formula (6)
By SrC 2o 4+ SrF 2+ B 2o 3→ Sr 3b 6o 11f 2+ H 2o ↑+CO 2↑ reaction formula synthetic compound Sr 3b 6o 11f 2, concrete operation step carries out according to embodiment 1;
By the compound fluoroboric acid strontium Sr of synthesis 3b 6o 11f 2single-phase polycrystalline powder and fusing assistant Sr in molar ratio 3b 6o 11f 2: H 3bO 3: carry out mixture at PbO: NaF=1: 4: 1: 3, load in the opening platinum crucible of Φ 80mm × 80mm, put into crystal growing furnace, 900 DEG C are heated to the temperature rise rate of temperature 50 C/h, constant temperature 30 hours, be cooled to temperature 865 DEG C again, obtain the mixed molten liquid of fluoroboric acid strontium and fusing assistant, enter seed rod in melt fast, treat that it produces drift crystalline substance, constant temperature 0.5h floats crystalline substance and does not change, temperature 820 DEG C is slowly dropped to the speed of temperature 1 DEG C/h, seed rod is proposed liquid level, is down to room temperature with the speed of temperature 30 DEG C/h, fluoroboric acid strontium seed crystal can be obtained;
And then prepare the blend melt of fluoroboric acid strontium and fusing assistant, Sr in molar ratio 3b 6o 11f 2: H 3bO 3: carry out mixture at PbO: NaF=1: 4: 1: 3, loads in the opening platinum crucible of Φ 80mm × 80mm, put into crystal growing furnace, 900 DEG C are heated to the temperature rise rate of temperature 50 C/h, constant temperature 50 hours, then be cooled to temperature 875 DEG C, obtain the mixed molten liquid of fluoroboric acid strontium and fusing assistant;
The seed crystal of acquisition is fixed on seed rod, seed crystal from crystal growing furnace top, first preheating seed crystal 45 minutes, then declining stretches into as in blend melt, be cooled to temperature 865 DEG C, with the rotating speed rotary seed crystal rod of 50rpm, with the speed slow cooling of temperature 1.5 DEG C/d to crystal desired size;
Arrive after required yardstick until single crystal growing, by crystal lift-off molten surface, be down to room temperature with the speed of temperature 30 DEG C/h, then crystal taken out from burner hearth, 25mm × 22mm × 17mm fluoroboric acid strontium crystal can be obtained.
SrC in raw material 2o 4can by corresponding SrCO 3, SrO, SrSO 4, SrSO 4, Sr (NO 3) 2or Sr (OH) 2substitute; B 2o 3can be substituted accordingly.
Embodiment 7:
For reaction formula (7), but be not limited to reaction formula (7)
By SrCO 3+ HF+H 3bO 3→ Sr 3b 6o 11f 2+ H 2o ↑+CO 2↑ synthetic compound Sr 3b 6o 11f 2, concrete operation step carries out as follows;
Take the SrCO of stoichiometric ratio 1mol 3, put into plastic beaker, add the HF solution of 3.0-4.0mol, slowly add, and stir with sticking plaster, after not having gas to produce, put it and enter in baking oven, be slowly warming up to 150 DEG C, constant temperature 24-36 hour, cooling, then take 2molSrCO 3, 6molH 3bO 3mix with dried material, and grind, load corundum crucible, put into retort furnace, be slowly warming up to 500 DEG C, constant temperature 3 hours, be cooled to grinding at room temperature even, take out crucible after cooling, by sample grinding evenly, be placed in crucible again, retort furnace is warming up to 630 DEG C, sample took out after 96 hours by constant temperature, put into mortar and smashed grinding to pieces and namely obtain fluoroboric acid strontium compound single-phase polycrystalline powder, again X-ray analysis is carried out to this polycrystal powder, gained X-ray spectrogram and finished product Sr 3b 6o 11f 2monocrystalline last X-ray spectrogram of pulverizing is consistent;
By the fluoroboric acid strontium Sr of synthesis 3b 6o 11f 2compound single-phase polycrystal powder and fusing assistant Sr in molar ratio 3b 6o 11f 2: H 3bO 3: carry out mixture at PbO: NaF=1: 4: 1: 3, load in the opening platinum crucible of Φ 80mm × 80mm, put into crystal growing furnace, 920 DEG C are heated to the temperature rise rate of temperature 20 DEG C/h, constant temperature 30 hours, be cooled to 870 DEG C again, obtain the mixed molten liquid of fluoroboric acid strontium and fusing assistant, enter seed rod in melt fast, treat that it produces drift crystalline substance, constant temperature 0.5h floats crystalline substance and does not change, temperature 830 DEG C is slowly dropped to the speed of temperature 2 DEG C/h, seed rod is proposed liquid level, is down to room temperature with the speed of temperature 40 DEG C/h, fluoroboric acid strontium seed crystal can be obtained;
And then prepare the blend melt of fluoroboric acid strontium and fusing assistant, Sr in molar ratio 3b 6o 11f 2: H 3bO 3: carry out mixture at PbO: NaF=1: 4: 1: 3, loads in the opening platinum crucible of Φ 80mm × 80mm, put into crystal growing furnace, 920 DEG C are heated to the temperature rise rate of temperature 20 DEG C/h, constant temperature 30 hours, then be cooled to temperature 870 DEG C, obtain the mixed molten liquid of fluoroboric acid strontium and fusing assistant;
The seed crystal of acquisition is fixed on seed rod, seed crystal from crystal growing furnace top, first preheating seed crystal 40 minutes, then decline and make the blend melt surface contact of seed crystal and fluoroboric acid strontium and fusing assistant, be cooled to 860 DEG C, with the rotating speed rotary seed crystal rod of 30rpm, with the speed slow cooling of temperature 3 DEG C/d to crystal desired size;
Arrive after required yardstick until single crystal growing, by crystal lift-off molten surface, be down to room temperature with the speed of temperature 30 DEG C/h, then crystal taken out from burner hearth, 21mm × 18mm × 11mm fluoroboric acid strontium crystal can be obtained.
SrCO in raw material 3can by corresponding Sr (OH) 2, SrCO 3, SrO, SrSO 4, SrSO 4, Sr (NO 3) 2or SrC 2o 4substitute; H 3bO 3can by corresponding B 2o 3substitute.
Embodiment 8:
By reaction formula Sr (NO 3) 2+ HF+B 2o 3→ Sr 3b 6o 11f 2+ NO 2↑+H 2o ↑ synthesis Sr 3b 6o 11f 2crystal, concrete operation step carries out according to embodiment 7;
By the fluoroboric acid strontium Sr of synthesis 3b 6o 11f 2compound single-phase polycrystal powder and fusing assistant Sr in molar ratio 3b 6o 11f 2: H 3bO 3: carry out mixture at PbO: NaF=1: 4: 1: 3, load in the opening platinum crucible of Φ 80mm × 80mm, put into crystal growing furnace, 930 DEG C are heated to the temperature rise rate of temperature 20 DEG C/h, constant temperature 30 hours, be cooled to 870 DEG C again, obtain the mixed molten liquid of fluoroboric acid strontium and fusing assistant, enter seed rod in melt fast, treat that it produces drift crystalline substance, constant temperature 0.5h floats crystalline substance and does not change, temperature 830 DEG C is slowly dropped to the speed of temperature 3 DEG C/h, seed rod is proposed liquid level, is down to room temperature with the speed of temperature 40 DEG C/h, fluoroboric acid strontium seed crystal can be obtained;
By the fluoroboric acid strontium Sr in molar ratio of synthesis 3b 6o 11f 2: H 3bO 3: carry out mixture at PbO: NaF=1: 4: 1: 3, loads in the opening platinum crucible of Φ 80mm × 80mm, put into crystal growing furnace, 930 DEG C are heated to the temperature rise rate of temperature 50 C/h, constant temperature 30 hours, then be cooled to temperature 870 DEG C, obtain the mixed molten liquid of fluoroboric acid strontium and fusing assistant;
The seed crystal of acquisition is fixed on seed rod, seed crystal from crystal growing furnace top, first preheating seed crystal 40 minutes, then decline and make the blend melt surface contact of seed crystal and fluoroboric acid strontium and fusing assistant, be cooled to 865 DEG C, with the rotating speed rotary seed crystal rod of 30rpm, with the speed slow cooling of temperature 3 DEG C/d to crystal desired size;
Arrive after required yardstick until single crystal growing, by crystal lift-off molten surface, be down to room temperature with the speed of temperature 20 DEG C/h, then crystal taken out from burner hearth, 25mm × 22mm × 18mm fluoroboric acid strontium crystal can be obtained.
Sr (NO in raw material 3) 2can by corresponding SrCO 3, Sr (OH) 2, SrCO 3, SrO, SrSO 4, SrSO 4or SrC 2o 4substitute; B 2o 3can by corresponding H 3bO 3substitute.
Embodiment 9:
By Sr (OH) 2+ HF+H 3bO 3→ Sr 3b 6o 11f 2+ H 2o ↑ synthesis Sr 3b 6o 11f 2crystal, concrete operation step carries out according to embodiment 7;
By the fluoroboric acid strontium Sr of synthesis 3b 6o 11f 2compound single-phase polycrystal powder and fusing assistant Sr in molar ratio 3b 6o 11f 2: H 3bO 3: carry out mixture at PbO: KF=1: 4: 1: 2, load in the opening platinum crucible of Φ 80mm × 80mm, put into crystal growing furnace, 920 DEG C are heated to the temperature rise rate of temperature 50 C/h, constant temperature 30 hours, be cooled to temperature 880 DEG C again, obtain the mixed molten liquid of fluoroboric acid strontium and fusing assistant, enter seed rod in melt fast, treat that it produces drift crystalline substance, constant temperature 0.5h floats crystalline substance and does not change, temperature 760 DEG C is slowly dropped to the speed of temperature 2 DEG C/h, seed rod is proposed liquid level, is down to room temperature with the speed of temperature 35 DEG C/h, fluoroboric acid strontium seed crystal can be obtained;
And then prepare the blend melt of fluoroboric acid strontium and fusing assistant, Sr in molar ratio 3b 6o 11f 2: H 3bO 3: carry out mixture at PbO: KF=1: 4: 1: 2, loads in the opening platinum crucible of Φ 80mm × 80mm, put into crystal growing furnace, 920 DEG C are heated to the temperature rise rate of temperature 50 C/h, constant temperature 30 hours, then be cooled to temperature 885 DEG C, obtain the mixed molten liquid of fluoroboric acid strontium and fusing assistant;
The seed crystal of acquisition is fixed on seed rod, seed crystal from crystal growing furnace top, first preheating seed crystal 50 minutes, then decline and make the blend melt surface contact of seed crystal and fluoroboric acid strontium and fusing assistant, be cooled to 878 DEG C, with the rotating speed rotary seed crystal rod of 50rpm, with the speed slow cooling of temperature 4 DEG C/d to crystal desired size;
Arrive after required yardstick until single crystal growing, by crystal lift-off molten surface, be down to room temperature with the speed of temperature 30 DEG C/h, then crystal taken out from burner hearth, 22mm × 17mm × 15mm fluoroboric acid strontium crystal can be obtained.
Sr (OH) in raw material 2can by corresponding SrCO 3, Sr (NO 3) 2, SrO, SrSO 4, SrSO 4or SrC 2o 4substitute; H 3bO 3can by corresponding B 2o 3substitute; In polycrystal synthesis, drug dosage is not limited to provided amount.
Embodiment 10:
According to reaction formula SrO+HF+B 2o 3→ Sr 3b 6o 11f 2+ H 2o ↑ synthetic compound Sr 3b 6o 11f 2, concrete operation step carries out according to embodiment 7;
By the fluoroboric acid strontium Sr of synthesis 3b 6o 11f 2compound single-phase polycrystal powder and fusing assistant Sr in molar ratio 3b 6o 11f 2: H 3bO 3: carry out mixture at PbO: LiF=1: 4: 1: 2, load in the opening platinum crucible of Φ 80mm × 80mm, put into crystal growing furnace, 910 DEG C are heated to the temperature rise rate of temperature 80 DEG C/h, constant temperature 30 hours, be cooled to temperature 875 DEG C again, obtain the mixed molten liquid of fluoroboric acid strontium and fusing assistant, enter seed rod in melt fast, treat that it produces drift crystalline substance, constant temperature 0.5h floats crystalline substance and does not change, temperature 600 DEG C is slowly dropped to the speed of temperature 2.5 DEG C/h, seed rod is proposed liquid level, is down to room temperature with the speed of temperature 30 DEG C/h, fluoroboric acid strontium seed crystal can be obtained;
And then prepare the blend melt of fluoroboric acid strontium and fusing assistant, Sr in molar ratio 3b 6o 11f 2: H 3bO 3: carry out mixture at PbO: LiF=1: 4: 1: 2, loads in the opening platinum crucible of Φ 80mm × 80mm, be heated to 910 DEG C, constant temperature 30 hours, then be cooled to temperature 880 DEG C, obtain the mixed molten liquid of fluoroboric acid strontium and fusing assistant with the temperature rise rate of temperature 80 DEG C/h;
The seed crystal of acquisition is fixed on seed rod, seed crystal from crystal growing furnace top, first preheating seed crystal 50 minutes, then decline and make the blend melt surface contact of seed crystal and fluoroboric acid strontium and fusing assistant, be cooled to 875 DEG C, with the rotating speed rotary seed crystal rod of 50rpm, with the speed slow cooling of temperature 4 DEG C/d to crystal desired size;
Arrive after required yardstick until single crystal growing, by crystal lift-off molten surface, be down to room temperature with the speed of temperature 30 DEG C/h, then crystal taken out from burner hearth, 20mm × 17mm × 11mm fluoroboric acid strontium crystal can be obtained.
SrO in raw material can by corresponding SrCO 3, Sr (NO 3) 2, Sr (OH) 2, SrSO 4, SrSO 4or SrC 2o 4substitute; B 2o 3can by corresponding H 3bO 3substitute.
Embodiment 11:
According to reaction formula SrC 2o 4+ HF+H 3bO 3→ Sr 3b 6o 11f 2+ H 2o ↑+CO 2↑ synthetic compound Sr 3b 6o 11f 2, concrete operation step carries out according to embodiment 7;
By the fluoroboric acid strontium Sr of synthesis 3b 6o 11f 2compound single-phase polycrystal powder and fusing assistant Sr in molar ratio 3b 6o 11f 2: H 3bO 3: carry out mixture at PbO: NaF=1: 4: 1: 3, load in the opening platinum crucible of Φ 80mm × 80mm, put into crystal growing furnace, 900 DEG C are heated to the temperature rise rate of temperature 35 DEG C/h, constant temperature 30 hours, be cooled to temperature 860 DEG C again, obtain the mixed molten liquid of fluoroboric acid strontium and fusing assistant, enter seed rod in melt fast, treat that it produces drift crystalline substance, constant temperature 0.5h floats crystalline substance and does not change, temperature 830 DEG C is slowly dropped to the speed of temperature 2.5 DEG C/h, seed rod is proposed liquid level, is down to room temperature with the speed of temperature 35 DEG C/h, fluoroboric acid strontium seed crystal can be obtained;
And then prepare the blend melt of fluoroboric acid strontium and fusing assistant, Sr in molar ratio 3b 6o 11f 2: H 3bO 3: carry out mixture at PbO: NaF=1: 4: 1: 3, loads in the opening platinum crucible of Φ 80mm × 80mm, be heated to 930 DEG C, constant temperature 30 hours, then be cooled to temperature 870 DEG C, obtain the mixed molten liquid of fluoroboric acid strontium and fusing assistant with the temperature rise rate of temperature 35 DEG C/h;
The seed crystal of acquisition is fixed on seed rod, seed crystal from crystal growing furnace top, first preheating seed crystal 50 minutes, then decline and make the blend melt surface contact of seed crystal and fluoroboric acid strontium and fusing assistant, be cooled to 860 DEG C, with the rotating speed rotary seed crystal rod of 45rpm, with the speed slow cooling of temperature 3 DEG C/d to crystal desired size;
Arrive after required yardstick until single crystal growing, by crystal lift-off molten surface, be down to room temperature with the speed of temperature 30 DEG C/h, then crystal taken out from burner hearth, 36mm × 28mm × 15mm fluoroboric acid strontium crystal can be obtained.
SrC in raw material 2o 4can by corresponding SrO, SrCO 3, Sr (NO 3) 2, Sr (OH) 2, SrSO 4, SrSO 4or SrC 2o 4substitute; H 3bO 3can by corresponding B 2o 3substitute; In polycrystal synthesis, drug dosage is not limited to provided amount.
Embodiment 12
By any crystal of gained in example 1-11, by being placed in shown in accompanying drawing on the position of 3, at room temperature, export with adjusting the 1064nm of QNd:YAG laser apparatus and make light source, observe obvious 532nm frequency doubling green light and export, output intensity is about 3 times of equal conditions KDP; Sending wavelength with adjusting QNd:YAG laser apparatus 1 is that the infrared beam of 1064nm injects Sr3B6O11F2 crystal 3 through convex lens 2, produce the green frequency doubled light that wavelength is 532nm, outgoing beam 4 is the infrared light of 1064nm and the green glow of 532nm containing wavelength, filter plate 5 elimination infrared light composition, obtains the green laser that wavelength is 532nm.

Claims (3)

1. a preparation method for fluoroboric acid strontium non-linear optic crystal, it is characterized in that adopting flux method to prepare crystal, concrete operation step follows these steps to carry out:
A, mortar will be put into by chemical formula metering than taking containing strontium, fluorine-containing, boron-containing compound, mixing carefully grinding, loading corundum crucible, put into retort furnace, be slowly warming up to 300 DEG C, constant temperature 3 hours, be cooled to grinding at room temperature even, be slowly warming up to 450 DEG C, gas drained only, take out crucible after cooling, by sample grinding evenly, then be placed in crucible, retort furnace is warming up to 630 DEG C, after constant temperature 72-96 hour, sample is taken out, put into mortar and smash grinding to pieces, obtain fluoroboric acid strontium Sr 3b 6o 11f 2compound single-phase polycrystal powder, then X-ray analysis is carried out to this polycrystal powder;
B, by the fluoroboric acid strontium Sr in step a 3b 6o 11f 2compound single-phase polycrystal powder and fusing assistant PbO, H 3bO 3, LiF or NaF or KF mix, 890-940 DEG C is heated to the temperature rise rate of temperature 30-80 DEG C/h, constant temperature 20-30 hour, be cooled to 860-880 DEG C again, obtain mixed molten liquid, under temperature 840-860 DEG C of condition, seed rod is entered in melt fast, treat that it produces drift crystalline substance, constant temperature 0.5h floats crystalline substance and does not change, and then slowly drops to temperature 830 DEG C with the speed of temperature 0.5-2 DEG C/h, then seed rod is proposed liquid level, be down to room temperature with the speed of temperature 10-50 DEG C/h, fluoroboric acid strontium Sr can be obtained 3b 6o 11f 2seed crystal, wherein fluoroboric acid strontium Sr 3b 6o 11f 2with fusing assistant H 3bO 3, the mol ratio of PbO, LiF or NaF or KF is 1: 4: 1: 2-3;
C, prepare fluoroboric acid strontium Sr by step b again 3b 6o 11f 2with fusing assistant carry out mixture, load in the opening platinum crucible of Φ 80mm × 80mm, put into crystal growing furnace, 890-940 DEG C is heated to the temperature rise rate of temperature 30-80 DEG C/h, constant temperature 20-30 hour, then be cooled to temperature 860-880 DEG C, obtain the mixed molten liquid of fluoroboric acid strontium and fusing assistant;
D, the seed crystal obtained by step b are fixed on seed rod, seed crystal from crystal growing furnace top, first preheating seed crystal 5-60 minute, then 840-860 DEG C is cooled to, make seed crystal and step c blend melt surface contact or stretch in blend melt, with the rotating speed rotary seed crystal rod of 20-50rpm, with the speed slow cooling of temperature 1-3 DEG C/d to crystal growth to desired size;
E, arrive after required yardstick until single crystal growing, by crystal lift-off molten surface, be down to room temperature with the speed of temperature 20-50 DEG C/h, then crystal taken out from burner hearth, fluoroboric acid strontium Sr can be obtained 3b 6o 11f 2non-linear optic crystal.
2. method according to claim 1, is characterized in that the compound containing strontium described in step a is Sr 2cO 3, Sr (NO 3) 2, SrO, Sr (OH) 2, SrC 2o 4or SrSO 4; Fluorine-containing compound is SrF 2, HF; Boron-containing compound is H 3bO 3or B 2o 3.
3. a purposes for the fluoroboric acid strontium non-linear optic crystal of method acquisition as claimed in claim 1, is characterized in that this crystal is for preparing times frequency generator, upper frequency transmodulator, lower frequency transmodulator or optical parametric oscillator.
CN201210293691.XA 2012-08-17 2012-08-17 The Preparation method and use of fluoroboric acid strontium non-linear optic crystal Active CN103590106B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201210293691.XA CN103590106B (en) 2012-08-17 2012-08-17 The Preparation method and use of fluoroboric acid strontium non-linear optic crystal

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201210293691.XA CN103590106B (en) 2012-08-17 2012-08-17 The Preparation method and use of fluoroboric acid strontium non-linear optic crystal

Publications (2)

Publication Number Publication Date
CN103590106A CN103590106A (en) 2014-02-19
CN103590106B true CN103590106B (en) 2015-11-25

Family

ID=50080413

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201210293691.XA Active CN103590106B (en) 2012-08-17 2012-08-17 The Preparation method and use of fluoroboric acid strontium non-linear optic crystal

Country Status (1)

Country Link
CN (1) CN103590106B (en)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN108683072A (en) * 2018-05-18 2018-10-19 北方工业大学 A method of improving SBO deep ultraviolet double-frequency laser delivery efficiencies

Families Citing this family (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105316763B (en) * 2014-05-27 2018-03-09 中国科学院新疆理化技术研究所 Compound fluoboric acid cadmium lead and fluoboric acid cadmium lead nonlinear optical crystal and preparation method and purposes
CN107217301B (en) * 2016-03-22 2019-04-12 中国科学院新疆理化技术研究所 Compound lithium fluoroborate potassium and lithium fluoroborate nonlinear optical crystal of potassium and preparation method and purposes
CN106745022B (en) 2016-12-09 2018-11-09 中国科学院新疆理化技术研究所 Compound ammonium fluoroborate and ammonium fluoroborate nonlinear optical crystal and preparation method and purposes
CN106948003B (en) * 2017-04-03 2019-08-06 中国科学院新疆理化技术研究所 Compound potassium fluoborate and potassium fluoborate nonlinear optical crystal and preparation method and purposes
CN107937981B (en) * 2017-11-17 2019-08-30 中国科学院新疆理化技术研究所 Compound fluoboric acid strontium and fluoboric acid strontium nonlinear optical crystal and preparation method and purposes
CN110042465B (en) * 2018-01-17 2020-08-28 中国科学院福建物质结构研究所 Alkaline earth metal fluoroborate compounds, crystals thereof, process for producing the same and use thereof
CN108640124B (en) * 2018-05-04 2022-04-26 新疆维吾尔自治区产品质量监督检验研究院 Copper lead borate lithium compound, copper lead borate lithium optical crystal, preparation method and application thereof

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP3678335B2 (en) * 1998-05-18 2005-08-03 株式会社日本触媒 Lower alkane oxidative dehydrogenation catalyst and process for producing olefin

Non-Patent Citations (3)

* Cited by examiner, † Cited by third party
Title
Design and growth of new NLO crystals for UV light generation;Zhang-Gui Hu et al.;《Journal of Crystal Growth》;20050120;第275卷;第232-239页 *
New Second-Order NLO Materials Based on Polymeric Borate Clusters and GeO4 Tetrahedra: A Combined Experimental and Theoretical Study;Jian-Han Zhang et al.;《Inorganic Chemistry》;20110113;第50卷(第2期);第1973-1982页 *
一种具有倍频效应的新型硼酸盐化合物Pb2[B5O9]Br;王永疆 等;《中国化学会2008年中西部地区无机化学、化工学术交流会会议论文集》;20080801;第15-17页 *

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN108683072A (en) * 2018-05-18 2018-10-19 北方工业大学 A method of improving SBO deep ultraviolet double-frequency laser delivery efficiencies
CN108683072B (en) * 2018-05-18 2020-07-10 北方工业大学 Method for improving SBO deep ultraviolet frequency doubling laser output efficiency

Also Published As

Publication number Publication date
CN103590106A (en) 2014-02-19

Similar Documents

Publication Publication Date Title
CN103590106B (en) The Preparation method and use of fluoroboric acid strontium non-linear optic crystal
CN101514492B (en) Large size potassium strontium borate nonlinear optical crystal, preparation and use thereof
CN101545138B (en) Non-linear optical crystal-sodium beryllate borate, growth method and application thereof
CN101311370B (en) Large-sized bismuth zinc borate nonlinear optical crystal, preparation method and use
CN102978702B (en) Compound barium borofluoride, barium borofluoride non-linear optical crystal, and preparation method and use of the barium borofluoride non-linear optical crystal
CN101498040B (en) K3B6O10 Br nonlinear optical crystal, preparation and use
CN103361725B (en) Compound chloroboric acid lead barium and chloroboric acid lead barium nonlinear optical crystal and preparation method and purposes
CN101435108A (en) Large size nonlinear optical crystal lead bromoborate, and preparation and use thereof
CN103288058B (en) Li2In2GeSe6 compound and Li2In2GeSe6 nonlinear optical crystal as well as preparation methods and applications thereof
CN103361726B (en) Compound sodium phosphate lithium and sodium phosphate lithium non-linear optic crystal and preparation method and purposes
CN105668577A (en) K3Ba3Li2Al4B6O20F compound, K3Ba3Li2Al4B6O20F nonlinear optical crystal, preparation method and application thereof
CN103046113A (en) Compound lead borate and nonlinear optical crystal of lead borate, preparation method thereof and purpose thereof
CN101984151B (en) Di lithium tetra borate rubidium nonlinear optic crystal, preparation method and application thereof
CN103950912A (en) RbBa2(PO3)5 compound, RbBa2(PO3)5 nonlinear optical crystal as well as preparation method and application of crystal
CN105986318B (en) Boronic acid compound barium caesium and barium borate caesium nonlinear optical crystal and preparation method and purposes
CN103132145B (en) Strontium-potassium vanadium borate compound, strontium-potassium vanadium borate nonlinear optical crystal, and preparation method and use of the strontium-potassium vanadium borate nonlinear optical crystal
CN101984149B (en) Method for preparing large chlorine barium borate nonlinear optic crystal and application thereof
CN103803572A (en) Compound calcium lithium tetrafluoroborate, nonlinear optical crystal of calcium lithium tetrafluoroborate, and preparation method and use thereof
CN105332045A (en) Compound Pb0.78Ba8.22B18O36, Pb0.78Ba8.22B18O36 nonlinear optical crystal, preparation methods and application
CN103173859A (en) Cadmium sodium borophosphate compound, cadmium sodium borophosphate nonlinear optical crystal, preparation methods of compound and crystal, and use of crystal
CN105133016A (en) Preparation method and application of lithium vanadate nonlinear optical crystal
CN101974783B (en) Compound cesium lithium borate (CLBO) nonlinear optical crystal, preparation method and application thereof
CN103290479B (en) Li 2in 2siSe 6compound, Li 2in 2siSe 6non-linear optic crystal and method for making and purposes
CN104651933A (en) Chlorine barium borate, chlorine barium borate nonlinear optical crystal, and preparation method and uses of chlorine barium borate nonlinear optical crystal
CN102650075A (en) Non-linear optical crystal cadmium fluoroborate

Legal Events

Date Code Title Description
C06 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
C14 Grant of patent or utility model
GR01 Patent grant