CN103757701A - Nonlinear optical crystal bismuth potassium iodide, and preparation method and application thereof - Google Patents
Nonlinear optical crystal bismuth potassium iodide, and preparation method and application thereof Download PDFInfo
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- CN103757701A CN103757701A CN201410058201.7A CN201410058201A CN103757701A CN 103757701 A CN103757701 A CN 103757701A CN 201410058201 A CN201410058201 A CN 201410058201A CN 103757701 A CN103757701 A CN 103757701A
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Abstract
The invention discloses a novel inorganic compound K2BiI5O15, and a preparation method, properties and application thereof as a second-order nonlinear optical crystal material. The outstanding characteristics of the material are that KIO4, KCl, Bi2O3 and H5IO6 are adopted as initial reactants for the first time to prepare the material in a hydrothermal method; the material has a stronger phase-matching second-order nonlinear optical effect, a broad light transmitting window in the visible region and the middle infrared region, a larger band gap and higher heat stability; the preparation method is easy to operate, high in raw material utilization rate, mild in experiment condition and high in product purity; the crystal material can be widely applied in the field of optics.
Description
Technical field
The present invention relates to a kind of mineral 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, can produce the non-linear optical effects such as frequency multiplication and frequency, difference frequency, optical parameter amplification.Utilize the second order nonlinear optical effect of crystal, can make the device for non-linear optical such as second harmonic generator, frequency converter, optical parametric oscillator, 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 that has dropped at present practical ultraviolet and visible region 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 practicalities.But for infrared non-linear optical material, from practicality, also has gap.Reason is existing infrared second-order non-linear optical crystal material, as AgGaS
2, AgGaSe
2and ZnGeP
2in crystal, although there is very large nonlinear second-order optical susceptibility, in infrared light district, also there is the very wide scope that sees through, but synthesis condition harshness, be not easy the large single crystal that growing optics quality is high, particularly damage threshold is lower, thereby can not meet the practical requirement of second-order non-linear optical crystal material.And the frequency inverted that realizes infrared laser has important value in fields such as national economy, national defense and military, as realize continuously adjustable molecular spectrum, widen the scope of laser radiation wavelength, open up new LASER Light Source etc.Thereby the research of 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 large, can realize phase matched, easily preparation and the good mineral crystal compound of stability and preparation method thereof.
Another object of the present invention is to provide the application as second-order non-linear optical crystal material of described mineral crystal compound.
Object of the present invention is achieved through the following technical solutions:
Described mineral crystal compound, its crystal space group is
abm2.
A method of preparing described mineral crystal compound, comprises the following steps: the KIO that is 6:6 ~ 12:1 ~ 2:6 ~ 12 by mol ratio
4, KCl, Bi
2o
3and H
5iO
6add in hydrothermal reaction kettle, then add distilled water to KIO
4ultimate density be 2 mol/L; Airtight hydrothermal reaction kettle is put into retort furnace, be heated to 225-230 ° of C, isothermal reaction is cooled to room temperature for 4 ~ 6 days again; After reaction finishes, product is placed in to ultrasonic cleaning machine distilled water wash, filters, then use alcohol flushing, obtain mineral crystal compound K
2biI
5o
15.
Described rate of temperature fall is 2 ~ 6 ° of C/h or naturally lowers the temperature and all can.
Described mineral 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 mineral crystal compound that the present invention makes has the following advantages and beneficial effect:
1. the mineral crystal compound that the present invention makes 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 mineral crystal compound that the present invention makes has the very wide scope that sees through in visible region and mid-infrared light district, and the infrared light transmission scope of powder reaches 12 microns;
3. the mineral crystal compound that the present invention makes is not containing crystal water, and to air-stable, not deliquescence, and better heat stability, can realize phase matched;
4. the present invention utilizes hydro-thermal 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 to this.
By 6 mmol KIO
4, 6 mmol KCl, 1 mmol Bi
2o
3with 6 mmol H
5iO
6add in the hydrothermal reaction kettle of 23 mL, then add 3 mL distilled water to make KIO
4ultimate density be 2 mol/L; Airtight hydrothermal reaction kettle is put into retort furnace, through 3h, be heated to 225 ° of C, isothermal reaction is cooled to room temperature with the rate of temperature fall of 2 ° of C/h in 4 days again; After reaction finishes, product is placed in to ultrasonic cleaning machine distilled water wash, filters, then use alcohol flushing, obtain colourless rhabdolith particle K
2biI
5o
15.
Embodiment 2
By 6 mmol KIO
4, 12 mmol KCl, 1 mmol Bi
2o
3with 6 mmol H
5iO
6add in the hydrothermal reaction kettle of 23 mL, then add 3 mL distilled water to make KIO
4ultimate density be 2 mol/L; Airtight hydrothermal reaction kettle is put into retort furnace, through 3h, be heated to 230 ° of C, isothermal reaction is cooled to room temperature with the rate of temperature fall of 6 ° of C/h in 5 days again; After reaction finishes, product is placed in to ultrasonic cleaning machine distilled water wash, filters, then use alcohol flushing, obtain colourless rhabdolith particle K
2biI
5o
15.
Embodiment 3
By 6 mmol KIO
4, 6 mmol KCl, 1 mmol Bi
2o
3with 6 mmol H
5iO
6add in the hydrothermal reaction kettle of 23 mL, then add 3 mL distilled water to make KIO
4ultimate density be 2 mol/L; Airtight hydrothermal reaction kettle is put into retort furnace, through 3h, be heated to 228 ° of C, isothermal reaction is cooled to room temperature for 6 days more naturally; After reaction finishes, product is placed in to ultrasonic cleaning machine distilled water wash, filters, then use alcohol flushing, obtain colourless rhabdolith particle K
2biI
5o
15.
The frequency doubling property of the prepared mineral crystal compound of the present invention obtains by Kurtz powder frequency doubling testing method.Concrete operation step is as follows: first the colourless rhabdolith particle of gained is ground to form to granularity is the powder of 100～125 microns, then packing two sides into has in the sample pool of glass port, afterwards sample pool is placed in to the laser optical path of Nd:YAG pulsed laser as light source, utilizing wavelength is the fundamental frequency rayed sample pool of 1064 nanometers, granularity is about to the KDP monocrystal of 100 microns as standard specimen, and signal is shown on oscilloscope through photomultiplier.
The mineral crystal compound phase place matching test that the present invention is prepared: the powder (20～40 that the mineral crystal compound of gained is ground first respectively and is sieved into different grain size scope, 40～60, 60～80, 80～100, 100～125, 125～150, 150～200, 200～300, 300～400, 400～500 microns), then packing two sides into has in the sample pool of glass port, afterwards sample pool is placed in to the laser optical path of Nd:YAG pulsed laser as light source, utilizing wavelength is the fundamental frequency rayed sample pool of 1064 nanometers, granularity is about to the KDP monocrystal of 100 microns as standard specimen, signal is shown on oscilloscope through photomultiplier.
The mineral crystal compound of gained is measured 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 mineral crystal compound absorbs spectrogram as shown in Figure 3, and as shown in Figure 4, this mineral crystal compound has larger optical band gap to its ATR-FTIR spectrogram, is about 3.53 eV; 12 microns of the infrared absorption Bian Keda of powder, as shown in Figure 5, this mineral 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.
The compound K that the present invention is prepared
2biI
5o
15crystalline structure in contain two independently K atoms, a Bi atom independently, three independently O atoms of I atom and eight independently.Wherein, each K atom and Bi atom form respectively the octoploids structure of distortion with eight O atoms; Two adjacent BiO
8octahedron interconnects by O2 atom, along C direction of principal axis, forms chain-like structure; And every two adjacent BiO
8between chain-like structure, pass through a kind of novel [I
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]
-[I (3) O with centre
3]
-by O7 bridging, get up.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 is all arranged regularly along C axle, and therefore the moment of dipole of these microcosmic can superpose effectively mutually, thereby produces a non-vanishing moment of dipole at C direction of principal axis.The arrangement mode of this uniqueness makes this compound in macroscopic view, show stronger non-linear optical effect.
In a word, it has good 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 can one skilled in the relevant art possessing, can also under the prerequisite that does not depart from aim of the present invention, make a variety of changes.
Claims (5)
1. a mineral crystal compound, is characterized in that, molecular formula is K
2biI
5o
15.
2. mineral crystal compound according to claim 1, is characterized in that, crystal space group is
abm2.
3. a method of preparing the mineral crystal compound described in claim 1 or 2, is characterized in that, comprises the following steps: the KIO that is 6:6 ~ 12:1 ~ 2:6 ~ 12 by mol ratio
4, KCl, Bi
2o
3and H
5iO
6add in hydrothermal reaction kettle, then add distilled water to KIO
4ultimate density be 2 mol/L; Airtight hydrothermal reaction kettle is put into retort furnace, be heated to 225-230 ° of C, isothermal reaction is cooled to room temperature for 4 ~ 6 days again; After reaction finishes, product is placed in to ultrasonic cleaning machine distilled water wash, filters, then use alcohol flushing, obtain mineral crystal compound K
2biI
5o
15.
4. the preparation method of mineral crystal compound according to claim 3, is characterized in that, described cooling method is nature cooling or the speed cooling with 2 ~ 6 ° of C/h.
5. mineral crystal compound claimed in claim 2 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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|---|---|---|---|
| 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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| CN103757701B CN103757701B (en) | 2015-12-30 |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104611769A (en) * | 2015-02-11 | 2015-05-13 | 武汉大学 | Intermediate infrared nonlinear optical crystal material RbIO2F2 as well as preparation method and application of crystal material |
| CN106757344A (en) * | 2016-12-29 | 2017-05-31 | 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 |
| CN109137072A (en) * | 2018-10-08 | 2019-01-04 | 武汉大学 | A kind of inorganic nonlinear optical crystal bismuth iodate sodium and its preparation and application |
| 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 Bi2I4O13 and preparation method as well as use thereof |
-
2014
- 2014-02-20 CN CN201410058201.7A patent/CN103757701B/en not_active Expired - Fee Related
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 Bi2I4O13 and preparation method as well as use thereof |
Non-Patent Citations (3)
| Title |
|---|
| BACHIR BENTRIA ET AL.: "Crystal structure of anhydrous bismuth iodate, Bi(IO3)3", 《JOURNAL OF CHEMICAL CRYSTALLOGRAPHY》 * |
| ZHENBO CAO ET AL.: "Bi2(IO4)(IO3)3: A New Potential Infrared Nonlinear Optical Material Containing [IO4]3-; Anion", 《INORGANIC CHEMISTRY》 * |
| 曹振博等: "BiIO4:一种新型红外非线性光学晶体", 《人工晶体学报》 * |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104611769A (en) * | 2015-02-11 | 2015-05-13 | 武汉大学 | Intermediate infrared nonlinear optical crystal material RbIO2F2 as well as preparation method and application of crystal material |
| 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 |
| CN106757344A (en) * | 2016-12-29 | 2017-05-31 | 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 |
| CN109137072A (en) * | 2018-10-08 | 2019-01-04 | 武汉大学 | A kind of inorganic nonlinear optical crystal bismuth iodate sodium and its preparation and application |
| 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 |
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| CN103757701B (en) | 2015-12-30 |
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