CN110129876A - Compound lead boron oxygen iodine and lead boron oxygen iodine nonlinear optical crystal and preparation method and purposes - Google Patents
Compound lead boron oxygen iodine and lead boron oxygen iodine nonlinear optical crystal and preparation method and purposes Download PDFInfo
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- CN110129876A CN110129876A CN201910452477.6A CN201910452477A CN110129876A CN 110129876 A CN110129876 A CN 110129876A CN 201910452477 A CN201910452477 A CN 201910452477A CN 110129876 A CN110129876 A CN 110129876A
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- boron oxygen
- nonlinear optical
- oxygen iodine
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- 239000013078 crystal Substances 0.000 title claims abstract description 64
- 230000003287 optical effect Effects 0.000 title claims abstract description 51
- QPLOHVWQOIMWTP-UHFFFAOYSA-N [I].[O].[B] Chemical compound [I].[O].[B] QPLOHVWQOIMWTP-UHFFFAOYSA-N 0.000 title claims abstract description 44
- 150000001875 compounds Chemical class 0.000 title claims abstract description 24
- 238000002360 preparation method Methods 0.000 title claims abstract description 15
- 238000006243 chemical reaction Methods 0.000 claims abstract description 17
- 239000000126 substance Substances 0.000 claims abstract description 15
- 238000000034 method Methods 0.000 claims abstract description 11
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 25
- FVAUCKIRQBBSSJ-UHFFFAOYSA-M sodium iodide Chemical compound [Na+].[I-] FVAUCKIRQBBSSJ-UHFFFAOYSA-M 0.000 claims description 18
- 239000000243 solution Substances 0.000 claims description 11
- 238000011109 contamination Methods 0.000 claims description 9
- 239000008367 deionised water Substances 0.000 claims description 9
- 229910021641 deionized water Inorganic materials 0.000 claims description 9
- 238000001914 filtration Methods 0.000 claims description 9
- WFUBYPSJBBQSOU-UHFFFAOYSA-M rubidium iodide Chemical compound [Rb+].[I-] WFUBYPSJBBQSOU-UHFFFAOYSA-M 0.000 claims description 6
- 235000009518 sodium iodide Nutrition 0.000 claims description 6
- 239000011259 mixed solution Substances 0.000 claims description 5
- UKFWSNCTAHXBQN-UHFFFAOYSA-N ammonium iodide Chemical compound [NH4+].[I-] UKFWSNCTAHXBQN-UHFFFAOYSA-N 0.000 claims description 4
- FPHIOHCCQGUGKU-UHFFFAOYSA-L difluorolead Chemical compound F[Pb]F FPHIOHCCQGUGKU-UHFFFAOYSA-L 0.000 claims description 4
- HSZCZNFXUDYRKD-UHFFFAOYSA-M lithium iodide Chemical compound [Li+].[I-] HSZCZNFXUDYRKD-UHFFFAOYSA-M 0.000 claims description 4
- XZXYQEHISUMZAT-UHFFFAOYSA-N 2-[(2-hydroxy-5-methylphenyl)methyl]-4-methylphenol Chemical compound CC1=CC=C(O)C(CC=2C(=CC=C(C)C=2)O)=C1 XZXYQEHISUMZAT-UHFFFAOYSA-N 0.000 claims description 2
- UNMYWSMUMWPJLR-UHFFFAOYSA-L Calcium iodide Chemical compound [Ca+2].[I-].[I-] UNMYWSMUMWPJLR-UHFFFAOYSA-L 0.000 claims description 2
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 2
- 229940107816 ammonium iodide Drugs 0.000 claims description 2
- SGUXGJPBTNFBAD-UHFFFAOYSA-L barium iodide Chemical compound [I-].[I-].[Ba+2] SGUXGJPBTNFBAD-UHFFFAOYSA-L 0.000 claims description 2
- 229910001638 barium iodide Inorganic materials 0.000 claims description 2
- 229940075444 barium iodide Drugs 0.000 claims description 2
- 229910052810 boron oxide Inorganic materials 0.000 claims description 2
- XQPRBTXUXXVTKB-UHFFFAOYSA-M caesium iodide Chemical compound [I-].[Cs+] XQPRBTXUXXVTKB-UHFFFAOYSA-M 0.000 claims description 2
- 229910001640 calcium iodide Inorganic materials 0.000 claims description 2
- 229940046413 calcium iodide Drugs 0.000 claims description 2
- JKWMSGQKBLHBQQ-UHFFFAOYSA-N diboron trioxide Chemical compound O=BOB=O JKWMSGQKBLHBQQ-UHFFFAOYSA-N 0.000 claims description 2
- ZASWJUOMEGBQCQ-UHFFFAOYSA-L dibromolead Chemical compound Br[Pb]Br ZASWJUOMEGBQCQ-UHFFFAOYSA-L 0.000 claims description 2
- 229940046892 lead acetate Drugs 0.000 claims description 2
- RQQRAHKHDFPBMC-UHFFFAOYSA-L lead(ii) iodide Chemical compound I[Pb]I RQQRAHKHDFPBMC-UHFFFAOYSA-L 0.000 claims description 2
- 238000003756 stirring Methods 0.000 claims description 2
- 238000010792 warming Methods 0.000 claims description 2
- 238000005660 chlorination reaction Methods 0.000 claims 1
- PIJPYDMVFNTHIP-UHFFFAOYSA-L lead sulfate Chemical compound [PbH4+2].[O-]S([O-])(=O)=O PIJPYDMVFNTHIP-UHFFFAOYSA-L 0.000 claims 1
- 230000005540 biological transmission Effects 0.000 abstract description 3
- 239000002994 raw material Substances 0.000 abstract description 3
- 239000003153 chemical reaction reagent Substances 0.000 abstract description 2
- 230000001988 toxicity Effects 0.000 abstract description 2
- 231100000419 toxicity Toxicity 0.000 abstract description 2
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 22
- 229910001868 water Inorganic materials 0.000 description 16
- 239000000463 material Substances 0.000 description 8
- 238000010438 heat treatment Methods 0.000 description 7
- 238000005516 engineering process Methods 0.000 description 6
- 239000007836 KH2PO4 Substances 0.000 description 4
- 238000011161 development Methods 0.000 description 4
- 229910000402 monopotassium phosphate Inorganic materials 0.000 description 4
- GNSKLFRGEWLPPA-UHFFFAOYSA-M potassium dihydrogen phosphate Chemical compound [K+].OP(O)([O-])=O GNSKLFRGEWLPPA-UHFFFAOYSA-M 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 3
- 235000019796 monopotassium phosphate Nutrition 0.000 description 3
- 239000002178 crystalline material Substances 0.000 description 2
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 2
- 239000004810 polytetrafluoroethylene Substances 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- XGCTUKUCGUNZDN-UHFFFAOYSA-N [B].O=O Chemical compound [B].O=O XGCTUKUCGUNZDN-UHFFFAOYSA-N 0.000 description 1
- 230000001427 coherent effect Effects 0.000 description 1
- 238000004891 communication Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 230000010365 information processing Effects 0.000 description 1
- 229910052740 iodine Inorganic materials 0.000 description 1
- 239000011630 iodine Substances 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- HWSZZLVAJGOAAY-UHFFFAOYSA-L lead(II) chloride Chemical compound Cl[Pb]Cl HWSZZLVAJGOAAY-UHFFFAOYSA-L 0.000 description 1
- 231100000572 poisoning Toxicity 0.000 description 1
- 230000000607 poisoning effect Effects 0.000 description 1
- -1 polytetrafluoroethylene Polymers 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 238000000844 transformation Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B35/00—Boron; Compounds thereof
- C01B35/08—Compounds containing boron and nitrogen, phosphorus, oxygen, sulfur, selenium or tellurium
- C01B35/10—Compounds containing boron and oxygen
- C01B35/12—Borates
- C01B35/127—Borates of heavy metals
-
- C—CHEMISTRY; METALLURGY
- C30—CRYSTAL GROWTH
- C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
- C30B29/00—Single crystals or homogeneous polycrystalline material with defined structure characterised by the material or by their shape
- C30B29/10—Inorganic compounds or compositions
- C30B29/12—Halides
-
- C—CHEMISTRY; METALLURGY
- C30—CRYSTAL GROWTH
- C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
- C30B7/00—Single-crystal growth from solutions using solvents which are liquid at normal temperature, e.g. aqueous solutions
- C30B7/10—Single-crystal growth from solutions using solvents which are liquid at normal temperature, e.g. aqueous solutions by application of pressure, e.g. hydrothermal processes
-
- G—PHYSICS
- G02—OPTICS
- G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
- G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
- G02F1/35—Non-linear optics
- G02F1/355—Non-linear optics characterised by the materials used
- G02F1/3551—Crystals
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
- C01P2002/77—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by unit-cell parameters, atom positions or structure diagrams
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Physics & Mathematics (AREA)
- Crystallography & Structural Chemistry (AREA)
- Nonlinear Science (AREA)
- Inorganic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- General Physics & Mathematics (AREA)
- Optics & Photonics (AREA)
- Crystals, And After-Treatments Of Crystals (AREA)
Abstract
The present invention relates to a kind of compound lead boron oxygen iodine and lead boron oxygen iodine nonlinear optical crystal and preparation method and purposes, which is Pb10O4(BO3)3I3, molecular weight 2693.14 prepared using hydro-thermal method, and products therefrom is directly crystal；The molecular formula of the crystal is Pb10O4(BO3)3I3, molecular weight 2693.14 belongs to monoclinic system, and space group Cc obtains lead boron oxygen iodine nonlinear optical crystal using hydro-thermal method.The crystal nonlinear optical effect is 0.1 times of KDP crystal, transmission region 361nm to 2600nm.The crystal growing process has easy to operate, at low cost, the advantages that reagent used is inorganic raw material, and toxicity is low, and growth cycle is short, and physico-chemical property is stablized.The lead boron oxygen iodine nonlinear optical crystal that the method obtains through the invention is used widely in the device for non-linear optical such as frequency-doubled conversion, optical parametric oscillator.
Description
Technical field
The present invention relates to a kind of compound lead boron oxygen iodine and lead boron oxygen iodine nonlinear optical crystal and preparation method and purposes,
Belong to domain of inorganic chemistry, also belongs to materials science field and optical field.
Technical background
The development of nonlinear optics and its crystalline material and the development of laser technology are closely related.In laser technology, directly
It connects that can be obtained laser wavelength using laser crystal limited, carries out frequency conversion using nonlinear optical crystal, it can will be complete
The laser of solid-state laser output is converted into new wave band of laser, so that the application range of laser is expanded significantly, in laser technology
There are huge application prospect and economic value in field.Nonlinear optical material is also the substance base of photoelectronic industry just because of this
Plinth is the mainstay of the fields such as Solid State Laser technology, optic communication and information processing development,
Up to the present, nonlinear optical material is extended to organic by inorganic, has block to develop to film, fiber and super
Lattice material.It is explored by decades, domestic and international researcher has found a series of nonlinear optical materials haveing excellent performance, such as
KDP, KB5, β-BBO, LBO, CBO, LN and KTP etc. have carried out large-scale production and have been applied widely.But these materials
In growing technology and upper also this certain limitation of application: if KDP and KB5 laser damage threshold is not high, being dissolved in water；β-BBO exists
There are phase transformations in growth course；CBO is easily deliquesced etc..And with the development of laser technology, laser light source further to deep ultraviolet,
Ultraviolet and infrared band is expanded, and which greatly enhances the demands of the nonlinear optical crystal to excellent combination property, therefore, is explored
Novel nonlinear optical crystal material has become research hotspot both domestic and external.
The problem to be solved by the invention is to provide a kind of transmission region is wider, there is second order nonlinear optical effect, it can
Realize phase matched, easy preparation and the preferable compound lead boron oxygen iodine non-linear optical crystal material of stability and its preparation side
Method and purposes.
Summary of the invention
To solve all-solid state laser system to the needs of the crystalline material with nonlinear optical effect, the object of the invention exists
In providing a kind of compound lead boron oxygen iodine, the compound chemical formula are as follows: Pb10O4(BO3)3I3, molecular weight 2693.14, using water
Thermal method preparation, products therefrom is directly crystal；
It is a further object of the present invention to provide a kind of compound lead boron oxygen iodine nonlinear optical crystal, which is
Pb10O4(BO3)3I3, molecular weight 2693.14 belongs to monoclinic system, space group Cc, and cell parameter is β=115.658 (1) °, Z=4；
It is yet another object of the invention to provide the purposes of compound lead boron oxygen iodine nonlinear optical crystal.
A kind of compound lead boron oxygen iodine of the present invention, the chemical formula of the compound are Pb10O4(BO3)3I3, molecular weight
It is 2693.14, is prepared using hydro-thermal method, products therefrom is crystal.
Compound lead boron oxygen iodine nonlinear optical crystal, the molecular formula of the crystal are Pb10O4(BO3)3I3, molecular weight is
2693.14, belong to monoclinic system, space group Cc, cell parameter is β=115.658 (1) °, Z=4.
The preparation method of the compound lead boron oxygen iodine nonlinear optical crystal, prepares crystal using hydro-thermal method, specific to grasp
It follows these steps to carry out:
A, PbO is added in the polytetrafluoroethyllining lining for the autoclave that volume is 25-125mL, H is added3BO3, then
KI is added, is eventually adding deionized water 4-50mL, mixes them thoroughly uniformly, obtains mixed liquor, wherein PbO, H3BO3It rubs with KI
You are than being 6-12:1-4:1-4；
B, mineralizer is added in the mixed solution in step a is PbF2、NH4I and PbI2, it stirs evenly, obtains mixed liquor,
The wherein molar ratio 0-2.5:4 of the additional amount of mineralizer and KI in step a；
C, the lid of the polytetrafluoroethyllining lining where mixed solution in step b is screwed, it is anti-is reloaded into corresponding high pressure
It answers in kettle, reaction kettle piston is screwed；
D, the autoclave in step c is placed in insulating box, is warming up to 150-230 DEG C, constant temperature for a period of time, then
It is cooled to room temperature；
E, autoclave is opened, transparent lead boron oxygen iodine nonlinear optics is arrived into the solution filtering containing crystal
Crystal.
PbO in step a can be replaced one in lead acetate, lead fluoride, lead bromide, lead chloride, plumbi nitras and lead oxalate
Kind is a variety of.
H in step a3BO3It can be replaced boron oxide.
KI in step a can be replaced lithium iodide, calcium iodide, barium iodide, cesium iodide, ammonium iodide, rubidium iodide and sodium iodide
One of or it is a variety of.
Solution is placed on clean free of contamination autoclave in step c.
The lead boron oxygen iodine nonlinear optical crystal is in preparation times frequency generator, up or down frequency converter or optical parameter
Purposes in oscillator.
A kind of compound lead boron oxygen iodine nonlinear optical crystal of the present invention, the molecular formula of the crystal are Pb10O4
(BO3)3I3, molecular weight 2693.14 belongs to monoclinic system, space group Cc, and cell parameter is β=115.658 (1) °, Z=4, powder times
Frequency effect reaches KDP (KH2PO4) 0.1 times, have wider transparency range, within the scope of the 361-2600nm of UV, visible light region
Still there is higher transmission.The preparation of this crystal is simple, and growth cycle is short, and used starting material toxicity is low small to human body murder by poisoning.
The preparation method of the compound lead boron oxygen iodine nonlinear optical crystal used in the present invention is hydro-thermal method, will be risen
After beginning raw material proportionally mixes, by the reaction kettle high temperature reaction under high pressure of sealing in certain temperature range, pass through program
Transparent lead boron oxygen iodine nonlinear optical crystal can be obtained in the method for cooling or constant temperature.
It is several typical available Pb below10O4(BO3)3I3The chemical equation of compound:
(1)10PbO+3H3BO3+2KI+NH4I→Pb10O4(BO3)3I3+NH4 ++K++H2O
(2)6PbO+1.5B2O3+4RbI+2.5PbF2→Pb10O4(BO3)3I3+F-+Rb++H2O
(3)7PbO+H3BO3+2KI→Pb10O4(BO3)3I3+K++H2O
(4)12PbO+2H3BO3+4NaI+0.5PbI2→Pb10O4(BO3)3I3+Na++H2O
(5)8(CH3COO)2Pb+2.5H3BO3+4KI+0.5PbI2→Pb10O4(BO3)3I3+K++H2O
(6)6PbF2+2H3BO3+4CsI+2PbI2→Pb10O4(BO3)3I3+F-+Cs++H2O
(7)10PbO+3H3BO3+4NaI+2PbI2→Pb10O4(BO3)3I3+Na++H2O
Raw material is to use commercially available reagent in the present invention, and the crystal that the method obtains through the invention is transparent, is had
Easy to operate, the speed of growth is fast, and growth cycle is short, at low cost, the advantages that.
The compound lead boron oxygen iodine nonlinear optical crystal of the method preparation, which is used as, through the invention prepares nonlinear optical
Device, including production times frequency generator, up or down frequency converter and optical parametric oscillator are learned, described uses compound lead boron oxygen
The nonlinear device of iodine nonlinear optical crystal production includes that will transmit through at least a branch of incident fundamental wave to generate at least a branch of frequency
Different from the coherent light of incident light.
The compound lead boron oxygen iodine nonlinear optical crystal is to optical manufacturing precision without particular/special requirement.
Detailed description of the invention
Fig. 1 is X-ray diffracting spectrum of the invention.
Fig. 2 is the working principle diagram for the device for non-linear optical that the present invention makes, and is laser including (1), (2) are
Convex lens, (3) are lead boron oxygen iodine nonlinear optical crystal, and (4) are Amici prism, and (5) are filter plate, and ω is the frequency for reflecting light
Rate is equal to 3 times of incident light frequency or incident light frequency.
Specific embodiment
Below in conjunction with drawings and examples, the present invention is described in detail:
Embodiment 1
With chemical equation 2 (1) 10PbO+3H3BO3+2KI+NH4I→Pb10O4(BO3)3I3+NH4 ++K++H2O prepares chemical combination
Object lead boron oxygen iodine, specific steps are as follows:
A, PbO is first added to volume as the polytetrafluoroethyllining lining of the autoclave of 25mL by 10:3:2 in molar ratio
In, H is added3BO3And KI, deionized water 5mL is added, mixes them thoroughly uniformly, obtains mixed liquor；
B, mineralizer NH is added in the mixed liquor in step a4I, NH4The additional amount of I is the molar ratio 1:2 of KI in step a；
C, the polytetrafluoroethyllining lining lid where mixed liquor in step b is screwed, is reloaded into clean free of contamination high pressure
In reaction kettle, reaction kettle piston is screwed；
D, the autoclave in step c is placed in insulating box, rises to 150 DEG C with the heating rate of 20 DEG C/h, perseverance
Temperature 5 days, then be cooled to room temperature with the rate of temperature fall of 3 DEG C/h；
E, autoclave is opened, compound lead boron oxygen iodine is arrived into the solution filtering containing crystal, products therefrom is
Transparent crystal.
Embodiment 2
With chemical equation 6PbO+1.5B2O3+4RbI+2.5PbF2→Pb10O4(BO3)3I3+F-+Rb++H2O prepares chemical combination
Object lead boron oxygen iodine, concrete operations follow these steps to carry out:
It a, is in molar ratio that PbO is first added in the polytetrafluoroethylene (PTFE) for the autoclave that volume is 25mL by 6:1.5:4
In lining, B is added2O3And RbI, deionized water 4mL is added, mixes them thoroughly uniformly, obtains mixed liquor；
B, mineralizer PbF is added in the mixed liquor in step a2, PbF2Additional amount and the molar ratio of RbI in step a be
2.5:4；
C, the polytetrafluoroethyllining lining lid where mixed liquor in step b is screwed, it is anti-is packed into clean free of contamination high pressure
It answers in kettle, reaction kettle piston is screwed；
D, the autoclave in step c is placed in insulating box, rises to 180 DEG C with the heating rate of 30 DEG C/h, perseverance
Temperature 6 days, cooled to room temperature；
E, autoclave is opened, compound lead boron oxygen iodine is arrived into the solution filtering containing crystal, products therefrom is
Transparent crystal.
Embodiment 3
With chemical equation (3) 7PbO+H3BO3+2KI→Pb10O4(BO3)3I3+K++H2O prepares lead boron oxygen iodine nonlinear optical
Crystal is learned, specific steps are as follows:
A, KCl is first added to volume as the polytetrafluoroethyllining lining of the autoclave of 125mL by 7:1:2 in molar ratio
In, H is added3BO3And KI, deionized water 50mL is added, mixes them thoroughly uniformly, obtains mixed liquor；
B, the polytetrafluoroethyllining lining lid where mixed liquor in step a is screwed, is reloaded into clean free of contamination high pressure
In reaction kettle, reaction kettle piston is screwed；
C, the autoclave in step b is placed in insulating box, rises to 220 DEG C with the heating rate of 10 DEG C/h, perseverance
Temperature 5 days, then be cooled to room temperature with the rate of temperature fall of 3 DEG C/h；
D, autoclave is opened, lead boron oxygen iodine nonlinear optical crystal is arrived into the solution filtering containing crystal.
Embodiment 4
With chemical equation (4) 12PbO+2H3BO3+4NaI+0.5PbI2→Pb10O4(BO3)3I3+Na++H2O prepares lead boron
Oxygen iodine nonlinear optical crystal, concrete operations follow these steps to carry out:
A, in molar ratio it is polytetrafluoroethyllining lining that PbO is first added to the autoclave that volume is 25mL by 12:2:4
In, H is added3BO3And NaI, deionized water 5mL is added, mixes them thoroughly uniformly, obtains mixed liquor；
B, mineralizer PbI is added in the mixed liquor in step a2, PbI2Additional amount and the molar ratio of NaI in step a be
0.5:4；
C, the polytetrafluoroethyllining lining lid where mixed liquor in step b is screwed, it is anti-is packed into clean free of contamination high pressure
It answers in kettle, reaction kettle piston is screwed；
D, the autoclave in step c is placed in insulating box, rises to 230 DEG C with the heating rate of 10 DEG C/h, perseverance
Temperature 6 days, cooled to room temperature；
E, autoclave is opened, lead boron oxygen iodine nonlinear optical crystal is arrived into the solution filtering containing crystal.
Embodiment 5
With 8 (CH of chemical equation3COO)2Pb+2.5H3BO3+4KI+0.5PbI2→Pb10O4(BO3)3I3+K++H2O preparation
Lead boron oxygen iodine nonlinear optical crystal:
It a, is in molar ratio 8:2.5:4 first by (CH3COO)2Pb is added to the polytetrafluoro for the autoclave that volume is 50mL
In ethylene liner, H is added3BO3And KI, deionized water 20mL is added, mixes them thoroughly uniformly, obtains mixed liquor；
B, mineralizer PbI is added in step a and mixed liquor2, PbI2Additional amount and the molar ratio of KI in step a be
0.5:4；
C, the polytetrafluoroethyllining lining lid where mixed solution in step b is screwed, is packed into clean free of contamination high pressure
In reaction kettle, reaction kettle piston is screwed；
D, the autoclave in step c is placed in insulating box, rises to 200 DEG C with the heating rate of 30 DEG C/h, perseverance
Temperature 8 days, then be cooled to room temperature with the rate of temperature fall of 10 DEG C/h；
E, autoclave is opened, lead boron oxygen iodine nonlinear optical crystal is arrived into the solution filtering containing crystal.
Embodiment 6
With chemical equation 6PbF2+2H3BO3+4CsI+2PbI2→Pb10O4(BO3)3I3+F-+Cs++H2O prepares lead boron oxygen
Iodine nonlinear optical crystal:
It a, is in molar ratio 6:2:4 first by PbF2It is added to the polytetrafluoroethyllining lining for the autoclave that volume is 75mL
In, H is added3BO3And CsI, deionized water 30mL is added, mixes them thoroughly uniformly, obtains mixed liquor；
B, mineralizer PbI is added in the mixed liquor in step a2, PbI2Additional amount and step a in CsI molar ratio be 2:
4；
C, the polytetrafluoroethyllining lining lid where mixed liquor in step b is screwed, it is anti-is packed into clean free of contamination high pressure
It answers in kettle, reaction kettle piston is screwed；
D, the autoclave in step c is placed in insulating box, rises to 220 DEG C with the heating rate of 30 DEG C/h, perseverance
Temperature 5 days, then room temperature is down to the rate of temperature fall of 10 DEG C/h；
E, autoclave is opened, lead boron oxygen iodine nonlinear optical crystal is arrived into the solution filtering containing crystal.
Embodiment 7
With chemical equation 10PbO+3H3BO3+4NaI+2PbI2→Pb10O4(BO3)3I3+Na++Pb2++H2O prepares lead boron
Oxygen iodine nonlinear optical crystal:
A, in molar ratio it is polytetrafluoroethyllining lining that KCl is added to the autoclave that volume is 100mL by 10:3:4
In, H is added3BO3And NaI, deionized water 45mL is added, mixes them thoroughly uniformly, obtains mixed liquor；
B, mineralizer PbI is added in the mixed liquor in step a2, PbI2Additional amount and step a in NaI molar ratio be 2:
4；
C, the polytetrafluoroethyllining lining lid where mixed liquor in step b is screwed, it is anti-is packed into clean free of contamination high pressure
It answers in kettle, reaction kettle piston is screwed；
D, the autoclave in step c is placed in insulating box, rises to 220 DEG C with the heating rate of 30 DEG C/h, perseverance
Temperature 10 days, cooled to room temperature；
E, autoclave is opened, lead boron oxygen iodine nonlinear optical crystal is arrived into the solution filtering containing crystal.
Claims (8)
1. a kind of compound lead boron oxygen iodine, it is characterised in that the chemical formula of the compound is Pb10O4(BO3)3I3, molecular weight is
2693.14, it is prepared using hydro-thermal method, products therefrom is crystal.
2. a kind of compound lead boron oxygen iodine nonlinear optical crystal, it is characterised in that the molecular formula of the crystal is Pb10O4(BO3)3I3, molecular weight 2693.14 belongs to monoclinic system, space group Cc, and cell parameter is β=115.658 (1) °, Z=4.
3. the preparation method of lead boron oxygen iodine nonlinear optical crystal according to claim 2, it is characterised in that use hydro-thermal
Method prepares crystal, and concrete operations follow these steps to carry out:
A, PbO is added in the polytetrafluoroethyllining lining for the autoclave that volume is 25-125mL, H is added3BO3, add
KI is eventually adding deionized water 4-50mL, mixes them thoroughly uniformly, obtains mixed liquor, wherein PbO, H3BO3With KI molar ratio
For 6-12:1-4:1-4；
B, mineralizer is added in the mixed solution in step a is PbF2、NH4I, KI and PbI2, it stirs evenly, obtains mixed liquor,
The molar ratio 0-2.5:4 of KI in the additional amount and step a of middle mineralizer；
C, the lid of the polytetrafluoroethyllining lining where mixed solution in step b is screwed, is reloaded into corresponding autoclave
In, reaction kettle piston is screwed；
D, the autoclave in step c is placed in insulating box, is warming up to 150-230 DEG C, constant temperature for a period of time, then cools down
To room temperature；
E, autoclave is opened, transparent lead boron oxygen iodine nonlinear optical crystal is arrived into the solution filtering containing crystal.
According to the method for claim 3,4. the PbO in step a can be replaced lead acetate, lead fluoride, lead bromide, chlorination
One of lead, lead sulfate, plumbi nitras and lead oxalate are a variety of.
According to the method for claim 3,5. the H in step a3BO3It can be replaced boron oxide.
6. according to the method for claim 3, the KI in step a can be replaced lithium iodide, calcium iodide, barium iodide, cesium iodide,
One of ammonium iodide, rubidium iodide and sodium iodide are a variety of.
7. according to the method described in claim 3, it is characterized in that solution is placed on clean free of contamination reaction under high pressure in step c
Kettle.
8. lead boron oxygen iodine nonlinear optical crystal according to claim 2 turns in preparation times frequency generator, up or down frequency
Purposes in parallel operation or optical parametric oscillator.
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