CN109797432A - Second-order non-linear optical crystal dichloride bismuth sulfate potassium, synthetic method and application - Google Patents
Second-order non-linear optical crystal dichloride bismuth sulfate potassium, synthetic method and application Download PDFInfo
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- CN109797432A CN109797432A CN201910087612.1A CN201910087612A CN109797432A CN 109797432 A CN109797432 A CN 109797432A CN 201910087612 A CN201910087612 A CN 201910087612A CN 109797432 A CN109797432 A CN 109797432A
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Abstract
The invention discloses a kind of second-order non-linear optical crystal dichloride bismuth sulfate potassium, preparation method and use.The chemical formula of the crystal is KBiCl2SO4, molecular weight 415.04 belongs to rhombic system, and space group isP212121, cell parameter are as follows:a=7.2890(3)Å,b=6.3673(3)Å,c=15.3306 (7),α=90°,β=90°,γ=90°,Z=4,V=711.51(6)Å3.Crystal preparation of the invention is simple, and Yi Shixian pure phase preparation, demand suitable for mass production has many advantages, such as big frequency-doubled effect and phase matched, which can be used for making device for non-linear optical, 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 double salt KBiCl2SO4Crystal, synthetic method and its application on second nonlinear optic,
Belong to optical crystal material technical field.
Background technique
Frequency-doubled effect is a kind of common and important second nonlinear optic (NLO) effect, it refers to that a branch of frequency is ω's
When laser is by crystal with NLO effect, the frequency of emergent light becomes the effect of 2 ω.Wavelength can be obtained more using NLO effect
Short laser, to be applied in laser technology.Lot of documents shows: introducing Pb2+、Sn2+、As3+、Sb3+、Bi3+, Se4+With
Te4+Be conducive to obtain NLO crystal Deng the element with chemical activity lone pair electrons, such as contain Bi3+NLO crystal just
There is BiFSeO3、BiO(IO3)、Bi3TeBO9Deng.Literature survey shows that there are no contain Bi so far3+Sulfates NLO crystal
Report.
Summary of the invention
The object of the present invention is to provide a kind of dichloride bismuth sulfate potassium crystal, preparation method and use.
Dichloride bismuth sulfate potassium crystal provided by the invention, chemical formula KBiCl2SO4, molecular weight 415.04, list
Crystal belongs to rhombic system, and space group isP212121, cell parameter are as follows:a = 7.2890(3) Å, b = 6.3673(3) Å,c=15.3306 (7),α = 90°, β= 90°, γ=90 °,Z=4,V = 711.51(6) Å3。
KBiCl provided by the invention2SO4The synthesis step of crystal includes the following steps: bismuth subcarbonate, potassium chloride, sulphur
Acid and hydrochloric acid in molar ratio 1: 2: 2:2 in a reservoir mix after be added deionized water dissolving each component, be placed in 40 ~ 60 DEG C
Lower evaporation at constant temperature waits 7 ~ 15 days solution to evaporate, up to KBiCl after washing, drying2SO4Crystal.
The present invention provides KBiCl2SO4The purposes of crystal is used for the frequency conversion of laser device laser output.
The present invention also provides a kind of device for non-linear optical, wherein the device includes KBiCl of the present invention2SO4
Nonlinear optical crystal.
Preferably, the device for non-linear optical further includes laser etc..
Compared with prior art, the invention has the advantages that
(1) KBiCl2SO4Crystal yield is high, demand suitable for mass production.
(2) powder frequency doubling test result shows KBiCl2SO4With nonlinear optical property very outstanding.1064
Under nm laser excitation, its powder SHG effect size is 1.7 times of KDP, and is able to achieve phase matched.It is expected that it can also be used for
In the upper and lower lasers such as frequency converter or optical parametric oscillator.
(3) test of ultraviolet-visible-near-infrared diffusing reflectance spectra the result shows that, KBiCl provided by the invention2SO4Crystal
Band gap magnitude is 3.95 electron-volts.
(4) KBiCl2SO4Synthetic method is relatively simple, and reaction raw materials are cheap, and crystal structure is good, and purity is higher.
Detailed description of the invention
Fig. 1 is KBiCl2SO4The crystal structure schematic diagram of crystal.
Fig. 2 is KBiCl2SO4The X-ray powder diffraction figure of crystal.
Fig. 3 is the KBiCl under 1064 nm laser2SO4The frequency-doubled effect size figure of crystal and standard substance KDP.
Fig. 4 is the KBiCl under 1064 nm laser2SO4The NLO phase matched figure of crystal.
Fig. 5 is KBiCl2SO4Ultraviolet-visible-near-infrared of crystal diffuses spectrogram.
Specific embodiment
It is described in further detail with reference to the accompanying drawing.
One, KBiCl2SO4The synthesis of crystal:
By reactant bismuth subcarbonate (90 %), potassium chloride (99 %), the concentrated sulfuric acid (98%) and concentrated hydrochloric acid (36%) according to mole
It feeds intake, all substances is mixed in 100ml beaker, and deionized water, which is added, dissolves each component, reaches solution than 1:2:2:2
Clear state.
It places the beaker in 50 ± 5 DEG C of constant temperature of baking oven, solution is made slowly to volatilize.
It waits 12 days solution thoroughly to volatilize to finish, takes out beaker, with ethanol wash reactant, after dry, under the microscope
Separation can obtain rodlike, transparent KBiCl2SO4Crystal.
Fig. 1 is KBiCl2SO4The crystal structure figure of crystal, each Bi atom be pentacoordinate with two Cl atoms and
Three O atoms are connected to form [a BiCl2O3] defect it is octahedra, each S atom and four O atoms formation [SO4]2–Four
Face body, [BiCl2O3] defect octahedron and [SO4]2–Tetrahedron connects the spiral to be formed along the stretching, extension of the direction b by sharing O atom
Chain.K ion is present in except chain structure, and the charge of equilibrium compound.
Fig. 2 is KBiCl2SO4The powder diagram of crystal, in Fig. 2, upper curve is experimental data, and lower curve is simulation number
According to.Analyzing result proves that sample is the KBiCl of pure phase2SO4。
Single crystal X-ray diffraction test data proves: KBiCl2SO4It crystallizes in rhombic systemP212121, cell parameter are as follows:a
= 7.2890(3) Å, b = 6.3673(3) Å, c = 15.3306(7) Å, α= 90°, β= 90°, γ= 90°, Z
= 4, V = 711.51(6) Å3。
Two, KBiCl2SO4The nonlinear optical test of crystal:
The KBiCl of acquisition2SO4It is packed into sample stage after powder crystal sample and standard sample KDP sieving, is vertically disposed in specimen holder
On, so that it is generated second-harmonic generation with 1064 nm laser irradiation crystal prototypes.Record the KBiCl of each particle size range2SO4With
The second harmonic intensity of KDP crystal.
Fig. 3 is shown 210-250 under the laser of 1064 nmμThe KBiCl of m size2SO4It is big with the frequency-doubled effect of KDP
It is small, KBiCl2SO4Frequency-doubled effect size be about 1.7 times of KDP.
Fig. 4 shows the different size KBiCl under the laser of 1064 nm2SO4Frequency-doubled effect size, the results showed that its energy
Realize phase matched.
Fig. 5 shows KBiCl2SO4The energy gap of crystal is 3.95 electron-volts.
The working principle of device for non-linear optical of the present invention are as follows: at least a branch of incidence electromagnetic radiation is passed through at least one
Block KBiCl2SO4After nonlinear optical crystal, the output radiation that at least a branch of frequency is different from incidence electromagnetic radiation is generated.
Claims (4)
1. dichloride bismuth sulfate potassium crystal, which is characterized in that its chemical formula is KBiCl2SO4, molecular weight 415.04, monocrystalline
Body belongs to rhombic system, space group P212121, cell parameter are as follows: α=90 °, β=90 °, γ=90 °, Z=4,
2. the synthetic method of dichloride bismuth sulfate potassium crystal as described in claim 1, which comprises the steps of:
Deionized water dissolving each group is added after 1:2:2:2 is mixed in a reservoir in molar ratio for bismuth subcarbonate, potassium chloride, sulfuric acid and hydrochloric acid
Point, it is placed in evaporation at constant temperature at 40~60 DEG C, 7~15 days solution is waited to evaporate, up to the crystal after washing, drying.
3. the purposes of dichloride bismuth sulfate potassium crystal as described in claim 1, which is characterized in that be used for laser device laser
The frequency conversion of output.
4. a kind of device for non-linear optical, which is characterized in that including dichloride bismuth sulfate potassium crystal material as described in claim 1
Material.
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101089241A (en) * | 2006-06-13 | 2007-12-19 | 中国科学院福建物质结构研究所 | Growing method of potassium vanadate non-linear optical crystal |
| CN101775652A (en) * | 2010-02-08 | 2010-07-14 | 中国科学院理化技术研究所 | Preparation and application of K3Al2(PO4)3 non-linear optical crystal |
| CN103757701A (en) * | 2014-02-20 | 2014-04-30 | 武汉大学 | Nonlinear optical crystal bismuth potassium iodide, and preparation method and application thereof |
-
2019
- 2019-01-29 CN CN201910087612.1A patent/CN109797432A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101089241A (en) * | 2006-06-13 | 2007-12-19 | 中国科学院福建物质结构研究所 | Growing method of potassium vanadate non-linear optical crystal |
| CN101775652A (en) * | 2010-02-08 | 2010-07-14 | 中国科学院理化技术研究所 | Preparation and application of K3Al2(PO4)3 non-linear optical crystal |
| CN103757701A (en) * | 2014-02-20 | 2014-04-30 | 武汉大学 | Nonlinear optical crystal bismuth potassium iodide, and preparation method and application thereof |
Non-Patent Citations (1)
| Title |
|---|
| M. KHELIFI ET AL.: "Crystal structure of potassium bismuth dichloride sulfate, KBiCl2S04", 《NEW CRYSTAL STRUCTURES》 * |
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