CN103757701B - Non-linear optical crystal of iodic acid bismuth potassium and its preparation method and application - Google Patents
Non-linear optical crystal of iodic acid bismuth potassium and its preparation method and application Download PDFInfo
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- CN103757701B CN103757701B CN201410058201.7A CN201410058201A CN103757701B CN 103757701 B CN103757701 B CN 103757701B CN 201410058201 A CN201410058201 A CN 201410058201A CN 103757701 B CN103757701 B CN 103757701B
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Abstract
The invention discloses a kind of novel inorganic compound K
2biI
5o
15and preparation method thereof, performance and the application as second-order non-linear optical crystal material.The outstanding feature of this material is: first with KIO
4, KCl, Bi
2o
3and H
5iO
6for initial reactant, hydrothermal method is adopted to be prepared; Have stronger can the second order nonlinear optical effect of phase matched; Very large optical transmission window is had in visible region and mid-infrared light district; There is larger band gap and thermostability; Synthetic method is simple to operate, raw material availability is high, experiment condition is gentle, product purity is high; This crystalline material can be widely used in optical field.
Description
Technical field
The present invention relates to a kind of Inorganic crystal compound and its preparation method and application, belong to domain of inorganic chemistry, also belong to material science and optical field.
Background technology
Non-linear optical effect originates from the interaction of laser and medium.When laser is when having the Propagation of non-zero second order susceptibility, the non-linear optical effect such as frequency multiplication and frequency, difference frequency, optically erasing can be produced.Utilize the second order nonlinear optical effect of crystal, the device for non-linear optical such as second harmonic generator, frequency converter, optical parametric oscillator can be made, in various fields such as laser technology, atmospheric surveillance and national defense and military, have important using value.Inorganic Nonlinear Optical Materials occupies dominant position in the practical research of second-order non-linear optical materials.According to transmission region and the scope of application, inorganic second-order non-linear optical crystal material can be divided into ultraviolet region nonlinear optical material, visible region nonlinear optical material and infrared light district nonlinear optical material.The Inorganic Nonlinear Optical Materials having dropped into practical ultraviolet and visible region at present has beta-barium metaborate (BBO), lithium tetraborate (LBO), potassium primary phosphate (KDP), potassium titanium oxide phosphate (KTP) etc., substantially can meet the requirement of most of practicality.But for FTIR radiation transmittance, also have gap from practicality.Reason is existing infrared second-order non-linear optical crystal material, as AgGaS
2, AgGaSe
2and ZnGeP
2in crystal, although have very large nonlinear second-order optical susceptibility, also have very wide through scope in infrared light district, but synthesis condition is harsh, be not easy the large single crystal that growing optics quality is high, particularly damage threshold is lower, thus can not meet the practical requirement of second-order non-linear optical crystal material.And the frequency inverted realizing infrared laser has important value in the field such as national economy, national defense and military, as realized continuously adjustable molecular spectrum, widening the scope of laser radiation wavelength, opening up new LASER Light Source etc.Thus the research finding the infrared inorganic nonlinear optical material of high laser damage threshold has become an important topic of current nonlinear optical material research field.
Summary of the invention
Primary and foremost purpose of the present invention is to overcome the shortcoming of prior art with not enough, provides that a kind of transmission region is wider, nonlinear second-order optical susceptibility is comparatively large, can realize phase matched, easily preparation and good Inorganic crystal compound of stability and preparation method thereof.
Another object of the present invention is to provide described Inorganic crystal compound as the application of second-order non-linear optical crystal material.
Object of the present invention is achieved through the following technical solutions:
A kind of Inorganic crystal compound, molecular formula is K
2biI
5o
15.
Described Inorganic crystal compound, its crystal space group is
abm2.
Prepare a method for described Inorganic crystal compound, comprise the following steps: the KIO by mol ratio being 6:6 ~ 12:1 ~ 2:6 ~ 12
4, KCl, Bi
2o
3and H
5iO
6add in hydrothermal reaction kettle, then add distilled water to KIO
4ultimate density be 2mol/L; Airtight hydrothermal reaction kettle is put into retort furnace, is heated to 225-230 ° of C, isothermal reaction is cooled to room temperature in 4 ~ 6 days again; After reaction terminates, product is placed in ultrasonic cleaning machine distilled water wash, filters, then use alcohol flushing, namely obtain Inorganic crystal compound K
2biI
5o
15.
Described rate of temperature fall is 2 ~ 6 ° of C/h or Temperature fall.
Described Inorganic crystal compound is as the application of second-order non-linear optical crystal material.
The present invention prepares K
2biI
5o
15reaction equation as follows:
KIO
4+KCl+Bi
2O
3+H
5IO
6 K
2BiI
5O
15
The Inorganic crystal compound that the present invention obtains has the following advantages and beneficial effect:
1. the Inorganic crystal compound that the present invention obtains has larger frequency-doubled effect (SHG), and Kurtz powder frequency doubling test result shows that its powder SHG effect is approximately 3 times of potassium primary phosphate (KDP);
2. the Inorganic crystal compound that the present invention obtains has very wide through scope in visible region and mid-infrared light district, the infrared light transmission scope of powder reaches 12 microns;
3. the Inorganic crystal compound that the present invention obtains does not contain crystal water, and to air-stable, not deliquescence, and better heat stability, can realize phase matched;
4. the present invention utilizes Hydrothermal preparation method, have simple to operate, raw material availability is high, experiment condition is gentle and product purity advantages of higher.
Accompanying drawing explanation
Fig. 1 is K of the present invention
2biI
5o
15crystalline structure figure.
Fig. 2 is K of the present invention
2biI
5o
15in [I
3o
9]
3-the structure iron of bridge.
Fig. 3 is K of the present invention
2biI
5o
15pressed powder UV-Vis-NIR absorb spectrogram.
Fig. 4 is K of the present invention
2biI
5o
15aTR-FTIR spectrogram.
Fig. 5 is K of the present invention
2biI
5o
15thermal weight loss spectrogram.
Fig. 6 is K of the present invention
2biI
5o
15sHG size and granularity graph of relation.
Embodiment
Below in conjunction with specific embodiment and accompanying drawing, technical scheme of the present invention is described in further detail, but embodiments of the present invention are not limited thereto.
Embodiment 1
By 6mmolKIO
4, 6mmolKCl, 1mmolBi
2o
3and 6mmolH
5iO
6add in the hydrothermal reaction kettle of 23mL, then add 3mL distilled water and make KIO
4ultimate density be 2mol/L; Airtight hydrothermal reaction kettle is put into retort furnace, is heated to 225 ° of C through 3h, isothermal reaction is cooled to room temperature with the rate of temperature fall of 2 ° of C/h in 4 days again; After reaction terminates, product is placed in ultrasonic cleaning machine distilled water wash, filters, then use alcohol flushing, namely obtain colourless rhabdolith particle K
2biI
5o
15.
Embodiment 2
By 6mmolKIO
4, 12mmolKCl, 1mmolBi
2o
3and 6mmolH
5iO
6add in the hydrothermal reaction kettle of 23mL, then add 3mL distilled water and make KIO
4ultimate density be 2mol/L; Airtight hydrothermal reaction kettle is put into retort furnace, is heated to 230 ° of C through 3h, isothermal reaction is cooled to room temperature with the rate of temperature fall of 6 ° of C/h in 5 days again; After reaction terminates, product is placed in ultrasonic cleaning machine distilled water wash, filters, then use alcohol flushing, namely obtain colourless rhabdolith particle K
2biI
5o
15.
Embodiment 3
By 6mmolKIO
4, 6mmolKCl, 1mmolBi
2o
3and 6mmolH
5iO
6add in the hydrothermal reaction kettle of 23mL, then add 3mL distilled water and make KIO
4ultimate density be 2mol/L; Airtight hydrothermal reaction kettle is put into retort furnace, is heated to 228 ° of C through 3h, isothermal reaction 6 days again Temperature fall to room temperature; After reaction terminates, product is placed in ultrasonic cleaning machine distilled water wash, filters, then use alcohol flushing, namely obtain colourless rhabdolith particle K
2biI
5o
15.
The frequency doubling property of the Inorganic crystal compound prepared by the present invention is obtained by Kurtz powder frequency doubling testing method.Concrete operation step is as follows: first the colourless rhabdolith particle of gained is ground to form the powder that granularity is 100 ~ 125 microns, then loading two sides has in the sample pool of glass port, sample pool is placed in the laser optical path of Nd:YAG pulsed laser as light source afterwards, utilize wavelength be 1064 nanometers fundamental frequency light irradiate sample pool, granularity is about the KDP monocrystal of 100 microns as standard specimen, signal is shown on oscilloscope through photomultiplier.
Inorganic crystal compound phase matched test prepared by the present invention: the Inorganic crystal compound of gained is ground first respectively and is sieved into the powder (20 ~ 40 of different grain size scope, 40 ~ 60, 60 ~ 80, 80 ~ 100, 100 ~ 125, 125 ~ 150, 150 ~ 200, 200 ~ 300, 300 ~ 400, 400 ~ 500 microns), then loading two sides has in the sample pool of glass port, sample pool is placed in the laser optical path of Nd:YAG pulsed laser as light source afterwards, utilize wavelength be 1064 nanometers fundamental frequency light irradiate sample pool, granularity is about the KDP monocrystal of 100 microns as standard specimen, signal is shown on oscilloscope through photomultiplier.
The Inorganic crystal compound of gained measures through x-ray crystal structure, and its molecular formula is K
2biI
5o
15, spacer is
abm2; Unit cell parameters is a=8.2115 (5), b=23.2072 (15), c=8.1977 (5), α=β=γ=90.00 °; Its structural arrangement as shown in Figure 1.Fig. 2 is a kind of novel [I in this compound structure
3o
9]
3-the structure iron of bridge.The UV-Vis-NIR of this Inorganic crystal compound absorbs spectrogram as shown in Figure 3, and as shown in Figure 4, this Inorganic crystal compound has larger optical band gap to its ATR-FTIR spectrogram, is about 3.53eV; The infrared absorption Bian Keda of powder 12 microns, as shown in Figure 5, this Inorganic crystal compound just starts weightlessness to its thermal weight loss spectrogram after 450 ° of C, therefore has good thermostability.The test result of its SHG size and granularity relation curve as shown in Figure 6, shows that this compound can realize phase matched.
Compound K prepared by the present invention
2biI
5o
15crystalline structure in containing two independently K atoms, an independently Bi atom, three independently I atom and eight independently O atoms.Wherein, each K atom and Bi atom form with eight O atoms the octoploids structure distorted respectively; Two adjacent BiO
8octahedron is interconnected by O2 atom, forms chain-like structure along C direction of principal axis; And every two adjacent BiO
8by a kind of novel [I between chain-like structure
3o
9]
3-bridge couples together, this novel [I
3o
9]
3-bridge-like structure never occurred in iodate series compound before, and it is by two tops [I (1) O
3]
-with [I (3) O of centre
3]
-got up by O7 bridging.Should [I
3o
9]
3-bridge is a kind of non-centrosymmetrical structure, can produce the moment of dipole of a microcosmic, what is interesting is, each [I
3o
9]
3-bridge all arranges regularly along C axle, and therefore the moment of dipole of these microcosmic can superpose effectively mutually, thus produces a non-vanishing moment of dipole at C direction of principal axis.The arrangement mode of this uniqueness makes this compound macroscopically show stronger non-linear optical effect.
In a word, it has excellent over-all properties, can be used as second-order non-linear optical crystal material and is applied.
By reference to the accompanying drawings embodiments of the present invention are explained in detail above, but the present invention is not limited to described embodiment, in the ken that possesses of one skilled in the relevant art, can also can make a variety of changes under the prerequisite not departing from present inventive concept.
Claims (4)
1. an Inorganic crystal compound, is characterized in that, molecular formula is K
2biI
5o
15, crystal space group is Abm2.
2. prepare a method for Inorganic crystal compound according to claim 1, it is characterized in that, comprise the following steps: be the KIO of 6:6:1:6 by mol ratio
4, KCl, Bi
2o
3and H
5iO
6add in hydrothermal reaction kettle, then add distilled water to KIO
4ultimate density be 2mol/L; Airtight hydrothermal reaction kettle is put into retort furnace, is heated to 225-230 DEG C, isothermal reaction is cooled to room temperature in 4 ~ 6 days again; After reaction terminates, product is placed in ultrasonic cleaning machine distilled water wash, filters, then use alcohol flushing, namely obtain Inorganic crystal compound K
2biI
5o
15.
3. the preparation method of Inorganic crystal compound according to claim 2, is characterized in that, described cooling method is Temperature fall or lowers the temperature with the speed of 2 ~ 6 DEG C/h.
4. Inorganic crystal compound according to claim 1 is as the application of second-order non-linear optical crystal material.
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|---|---|---|---|
| CN201410058201.7A CN103757701B (en) | 2014-02-20 | 2014-02-20 | Non-linear optical crystal of iodic acid bismuth potassium and its preparation method and application |
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|---|---|---|---|
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| CN103757701B true CN103757701B (en) | 2015-12-30 |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104611769B (en) * | 2015-02-11 | 2017-02-01 | 武汉大学 | Intermediate infrared nonlinear optical crystal material RbIO2F2 as well as preparation method and application of crystal material |
| CN106757344B (en) * | 2016-12-29 | 2018-11-23 | 武汉大学 | Two kinds of inorganic fluoriodate crystal and its preparation method and application |
| CN108221053A (en) * | 2018-02-08 | 2018-06-29 | 中国科学院福建物质结构研究所 | The preparation of novel nonlinear optical crystal and purposes |
| CN109137072B (en) * | 2018-10-08 | 2020-04-10 | 武汉大学 | Inorganic nonlinear optical crystal sodium bismuth iodate and preparation and application thereof |
| CN109797432A (en) * | 2019-01-29 | 2019-05-24 | 扬州大学 | Second-order non-linear optical crystal dichloride bismuth sulfate potassium, synthetic method and application |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102808220A (en) * | 2011-05-31 | 2012-12-05 | 中国科学院理化技术研究所 | Nonlinear optical crystal Bi2I4O13And preparation method and application thereof |
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2014
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Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102808220A (en) * | 2011-05-31 | 2012-12-05 | 中国科学院理化技术研究所 | Nonlinear optical crystal Bi2I4O13And preparation method and application thereof |
Non-Patent Citations (4)
| Title |
|---|
| Anion.《inorganic Chemistry》.2011,第50卷 * |
| BiIO4:一种新型红外非线性光学晶体;曹振博等;《人工晶体学报》;20110831;第40卷(第4期);第858-861页 * |
| Crystal structure of anhydrous bismuth iodate, Bi(IO3)3;Bachir Bentria et al.;《Journal of Chemical Crystallography》;20031130;第33卷(第11期);第867-873页 * |
| Zhenbo Cao et al..Bi2(IO4)(IO3)3: A New Potential Infrared Nonlinear Optical Material Containing [IO4]3- * |
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