CN104962992A - Middle-infrared nonlinear optical crystal material KBi4F13, and preparation method and application thereof - Google Patents
Middle-infrared nonlinear optical crystal material KBi4F13, and preparation method and application thereof Download PDFInfo
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- CN104962992A CN104962992A CN201510269943.9A CN201510269943A CN104962992A CN 104962992 A CN104962992 A CN 104962992A CN 201510269943 A CN201510269943 A CN 201510269943A CN 104962992 A CN104962992 A CN 104962992A
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- optical crystal
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Abstract
The invention discloses a middle-infrared nonlinear optical crystal material. The chemical formula of the crystal material is KBi4F13, the crystal space group of the material is I-4, and cell parameters are characterized in that a is 0.92027(19)nm, b is 0.92027(19)nm, c is 0.62589(13)nm, alpha = beta = gamma = 90DEG, and Z is 2. The invention also provides a hydrothermal preparation method of the crystal material. The middle-infrared nonlinear optical crystal material prepared in the invention has a phase matching second harmonic generation (SHG) effect, and a Kurtz powder frequency multiplication test result shows that the powder frequency multiplication effect of the crystal material is same to that of potassium dihydrogen phosphate (KDP); the laser damage threshold of the powder is 120MW/cm<2>, and is above 23 times the laser damage threshold of present commercial middle-infrared nonlinear optical crystal materials AgGaS2; the middle-infrared nonlinear optical crystal material has a wide permeable range in visible light region and middle-infrared light region; the middle-infrared nonlinear optical crystal material has the advantages of no crystal water, stability to air, and good heat stability; and monocrystalline materials can be prepared through the hydrothermal method.
Description
Technical field
The invention belongs to domain of inorganic chemistry, particularly relate to infrared nonlinear optical crystal material and its preparation method and application in one.
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 a lot of fields, as aspects such as laser technology, atmospheric surveillance, national defense and military, important using value is had.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 nonlinear 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 BBO (beta-barium metaborate), LBO (lithium tetraborate), KDP (potassium primary phosphate), KTP (potassium titanium oxide phosphate) etc., substantially can meet the requirement of most of practicality.But for FTIR radiation transmittance, also have gap from practicality.Reason is existing FTIR radiation transmittance, as AgGaS
2, AgGaSe
2deng, 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 to grow up to the high monocrystalline of large optical quality, particularly damage threshold is lower, thus can not meet the practical requirement of non-linear optical crystal material.And the frequency inverted realizing mid-infrared laser has important value in the field such as national economy, national defence, as realized continuously adjustable molecular spectrum, realize 3 ~ 5 micron waveband continuous laser spectrum etc.Thus the research of infrared inorganic nonlinear optical material has become an important topic of current nonlinear optical material research field.In " non-linear optical crystal material science " book of Science Press's publication in 2003, clearly " in the spectral band of whole nonlinear optics; the non-linear optic crystal of infrared band is a weak link; therefore, have to be strengthened to the research of the novel frequency conversion crystal of this wave band " is proposed.
Summary of the invention
Problem to be solved by this invention is to provide one has comparatively high laser damage threshold, easily preparation and stability middle infrared nonlinear optical crystal material and its preparation method and application preferably.
Concrete technical scheme of the present invention is as follows:
Infrared nonlinear optical crystal material in one, its chemical formula is KBi
4f
13, crystal space group is I-4, and unit cell parameters is:
α=β=γ=90 °, Z=2.
Above-mentioned middle infrared nonlinear optical crystal material adopts hydro-thermal reaction legal system standby: by KF and Bi
2o
3be dissolved in the HF aqueous solution, carry out hydro-thermal reaction, namely obtain middle infrared nonlinear optical crystal material; The mole number of described KF is Bi
2o
3the twice of mole number.
The preparation method of above-mentioned middle infrared nonlinear optical crystal material, specifically comprises the following steps: be KF and Bi of 2:1 by mol ratio
2o
3join in hydrothermal reaction kettle, add the HF solution that massfraction is 40%; Put into retort furnace after being sealed by reactor, be heated to 230 DEG C in 3h, then isothermal reaction 3 days, Temperature fall 1 day, after reaction terminates, use distilled water wash product, suction filtration post-drying, obtain colourless block small-crystalline, be middle infrared nonlinear optical crystal material.
Described reactor, its liner is tetrafluoroethylene.
Described middle infrared nonlinear optical crystal material is in the application of optical field.
The present invention is with KF, Bi
2o
3be initial reactant with HF solution, be prepared middle infrared nonlinear optical crystal material by hydro-thermal reaction method.Experiment shows, the frequency-doubled effect of the middle infrared nonlinear optical crystal material powder in the present invention is 1 times of KDP; Phase matched can be realized; Full impregnated overrange is 0.27-14 micron; The laser damage threshold of powder is 120MW/cm
2; Thermal weight loss temperature is 220 DEG C.
Inorganic middle FTIR radiation transmittance KBi disclosed in this invention
4f
13with [Bi
4f
13]
-as anionic group, positively charged ion is alkalimetal ion K
+.The anionic group of this kind of compound is the [Bi of distortion
4f
13]
-configuration, and group forms non-centrosymmetry arrangement in crystal, thus be conducive to the geometric superposition of microcosmic second order nonlinear optical effect, show non-linear optical effect macroscopically.The spacer of this crystalline material is I-4, and unit cell parameters is
α=β=γ=90 °, Z=2.This compound containing crystal water, can not reach 14 microns in the transparency range of middle infrared; In ultraviolet-visible district, ABSORPTION EDGE observed value reaches 0.27 micron.There is very high laser damage threshold and non-linear optical effect and KDP suitable.In a word, it has excellent over-all properties, can be used as non-linear optical crystal material and is applied.
Compared with prior art, this inorganic middle infrared nonlinear optical crystal material that the present invention obtains has the following advantages:
1. have the frequency-doubled effect (SHG) of suitable energy phase matched, Kurtz powder frequency doubling test result shows that its powder SHG effect is suitable with potassium primary phosphate (KDP);
2. the laser damage threshold of the powder of compound is 120MW/cm
2, be the middle infrared nonlinear optical crystal material AgGaS of current commercialization
2(be 5.2MW/cm under equal test condition
2) 23 times of laser damage threshold.
3. the powder of this compound has wider through scope in visible region and mid-infrared light district, is 0.27 ~ 14 micron completely through wave band;
4. not containing crystal water, to air-stable, and better heat stability, thermal weight loss temperature reaches 220 degrees Celsius;
5. simple hydrothermal method can be utilized to prepare monocrystal material.
6. middle infrared nonlinear optical crystal material provided by the invention have strong can the second order nonlinear optical effect of phase matched, wider optical transmission window is had in visible region and infrared light district, there is very high laser damage threshold and thermostability, synthetic method is simple to operate, the reaction times is short, experiment condition is gentle, product purity is high, can be widely used in optical field.
Accompanying drawing explanation
Fig. 1 is KBi of the present invention
4f
13the structure cell accumulation graph of crystal;
Fig. 2 is KBi of the present invention
4f
13middle anionic group [Bi
4f
13]
-pareto diagram;
Fig. 3 is KBi of the present invention
4f
13the UV-visible-near infrared absorption of powder;
Fig. 4 is KBi of the present invention
4f
13the Fourier transform attenuated total reflectance attenuated total refraction infrared spectra of powder;
Fig. 5 is KBi of the present invention
4f
13the thermal weight loss collection of illustrative plates of powder;
Fig. 6 is KBi of the present invention
4f
13the frequency-doubled effect phase matched collection of illustrative plates of powder.
Embodiment
Below in conjunction with specific embodiment, technical scheme of the present invention is further described.
Embodiment 1:
KF (0.1162g, 2mmol) and Bi
2o
3(0.4660g, 1mmol) joins capacity is in the hydrothermal reaction kettle of 23mL, adds the HF solution that 3ml massfraction is 40%.After sealing, reactor is put into retort furnace, be heated to 230 DEG C through 3h, isothermal reaction 3d, temperature fall time 1d, after reaction terminates, use distilled water wash product, suction filtration post-drying, obtain colourless block small-crystalline, be middle infrared nonlinear optical crystal material.
Performance test:
Below correlation detection is carried out to infrared nonlinear optical crystal material prepared by embodiment 1:
(1) powder SHG effect experiment:
The frequency doubling property of infrared nonlinear optical crystal material is obtained by Kurtz-Perry powder frequency doubling testing method.Concrete operation step is as follows:
In embodiment 1 being prepared, infrared nonlinear optical crystal material grinds to form the powder that particle diameter is about 100 ~ 125 microns, then being contained in two sides has in the sample pool of glass port, afterwards sample pool is placed on laser optical path, the fundamental frequency light that use Nd:YAG pulsed laser is 1064 nanometers for light source generation wavelength injects sample pool, using the KDP monocrystal of particle diameter about 100 ~ 125 microns as standard specimen, signal is shown on oscilloscope through photomultiplier.Kurtz powder frequency doubling test result shows that the powder SHG effect of middle infrared nonlinear optical crystal material prepared by embodiment 1 is 1 times of KDP.
(2) RbIO
2f
2frequency-doubled effect can phase matched test:
In embodiment 1 being prepared, infrared nonlinear optical crystal material grinds respectively and is sieved into the powder (20 ~ 40 of different grain size scope, 40 ~ 60, 60 ~ 80, 80 ~ 100, 100 ~ 125, 125 ~ 150 and 150 ~ 200 microns), then being contained in two sides respectively has in the sample pool of glass port, afterwards sample pool is placed on laser optical path, the fundamental frequency light that use Nd:YAG pulsed laser is 1064 nanometers for light source generation wavelength injects sample pool, signal is shown on oscilloscope through photomultiplier, the frequency-doubled signal intensity size of test different-grain diameter, mapping post analysis judges that can the frequency-doubled effect of compound phase matched.
Fig. 1, Fig. 2 are KBi respectively
4f
13the structure cell accumulation graph of crystal, [Bi
4f
13]
-the Pareto diagram of anionic group.KBi
4f
13complicated structure, each Bi atom and 2 F1,2 F3,1 F2,1 F4 is connected, and wherein has the Bi-F key (2.153 (5)-2.220 (5) that three are shorter
), three longer Bi-F keys (are greater than 2.40
), so just make BiF
6group has a very large distortion, can produce the dipole moment of a microcosmic, and as can be seen from the figure four BiF
6the dipole moment of group is not offset completely, [the Bi therefore formed
4f
13]
-anionic group also has the moment of dipole of a microcosmic, as can be seen from the figure these four [Bi
4f
13]
-although anionic group is interconnected, the orientation in crystal space is consistent substantially, just because of such arrangement mode, just result in crystal dipole moment macroscopically, thus makes KBi
4f
13show non-linear optical effect to a certain degree.
Fig. 3 is the ultraviolet-visible light spectrogram of powdered material, and as can be seen from Figure 3, its ultraviolet absorption edge is at 0.27 micron, and the band gap size of calculating is 4.55 electron-volts.
Fig. 4 is the Fourier transform attenuated total reflectance attenuated total refraction infrared spectrogram of middle infrared nonlinear optical crystal material prepared by embodiment 1, as can be seen from infrared spectrogram, this material is without any absorption between 4000 wave number to 700 wave numbers, and this illustrates this material between 4000 wave number to 700 wave numbers all without absorption.The result of integrated UV-visible spectrum and infrared spectra, that can know this material by inference has wider transparency range, and its transparency range is 0.27 micron to 14 microns.The thermal analyses of this material and the test result of powder frequency doubling phase matched are shown in Fig. 5 and Fig. 6, as seen from Figure 5, this material just starts weightlessness more than 220 degrees Celsius, has good thermostability, as seen from Figure 6, the frequency-doubled effect of this material can phase matched.
Claims (7)
1. an infrared nonlinear optical crystal material in, is characterized in that: its chemical formula is KBi
4f
13, crystal space group is I-4, and unit cell parameters is:
α=β=γ=90 °, Z=2.
2. middle infrared nonlinear optical crystal material according to claim 1, is characterized in that: its powder SHG effect is 1 times of potassium primary phosphate; Full impregnated overrange is 0.27-14 micron.
3. middle infrared nonlinear optical crystal material according to claim 1 and 2, is characterized in that: the laser damage threshold of its powder is 120MW/cm
2, thermal weight loss temperature is 220 DEG C.
4. the preparation method of the middle infrared nonlinear optical crystal material described in any one of claim 1-3, is characterized in that, adopts hydro-thermal reaction legal system standby: by KF and Bi
2o
3be dissolved in the HF aqueous solution, carry out hydro-thermal reaction, namely obtain middle infrared nonlinear optical crystal material; The mole number of described KF is Bi
2o
3the twice of mole number.
5. the preparation method of middle infrared nonlinear optical crystal material according to claim 4, is characterized in that specifically comprising the following steps: be KF and Bi of 2:1 by mol ratio
2o
3join in hydrothermal reaction kettle, add the HF solution that massfraction is 40%; Put into retort furnace after being sealed by reactor, be heated to 230 DEG C in 3h, then isothermal reaction 3 days, Temperature fall 1 day, after reaction terminates, use distilled water wash product, suction filtration post-drying, obtain colourless block small-crystalline, be middle infrared nonlinear optical crystal material.
6. the preparation method of middle infrared nonlinear optical crystal material according to claim 5, is characterized in that: described reactor, its liner is tetrafluoroethylene.
7. the middle infrared nonlinear optical crystal material described in any one of claim 1-3 is in the application of optical field.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108360066A (en) * | 2018-02-07 | 2018-08-03 | 同济大学 | A kind of infrared nonlinear optical crystal mixes halogen bismuthic acid potassium and preparation method and application |
| CN109338471A (en) * | 2018-11-28 | 2019-02-15 | 同济大学 | A kind of mid-infrared light frequency-doubling crystal fluoro tungsten Potassiumiodate material and preparation and application |
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| CN1396318A (en) * | 2002-05-17 | 2003-02-12 | 武汉大学 | Non-linear infrared inorganic optical crystal and its preparing process |
| CN1888147A (en) * | 2006-06-05 | 2007-01-03 | 武汉大学 | Second-order non-linear optical crystal material and its synthesis process and use |
| CN101311353A (en) * | 2008-04-18 | 2008-11-26 | 武汉大学 | Second order nonlinear optical crystal material, preparation method and use thereof |
| 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 |
-
2015
- 2015-05-25 CN CN201510269943.9A patent/CN104962992B/en not_active Expired - Fee Related
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1396318A (en) * | 2002-05-17 | 2003-02-12 | 武汉大学 | Non-linear infrared inorganic optical crystal and its preparing process |
| CN1888147A (en) * | 2006-06-05 | 2007-01-03 | 武汉大学 | Second-order non-linear optical crystal material and its synthesis process and use |
| CN101311353A (en) * | 2008-04-18 | 2008-11-26 | 武汉大学 | Second order nonlinear optical crystal material, preparation method and use thereof |
| 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 |
Non-Patent Citations (2)
| Title |
|---|
| C BESKY JOB, ET AL.: "Growth,structural and microhardness studies of KSb2F7 and KSb4F13 crystals", 《INDIAN JOURNAL OF PURE & APPLIED PHYSICS》 * |
| 吴奇等: "KBi4F13一个具有高激光损伤阈值的中红外非线性光学材料", 《无机化学学报》 * |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108360066A (en) * | 2018-02-07 | 2018-08-03 | 同济大学 | A kind of infrared nonlinear optical crystal mixes halogen bismuthic acid potassium and preparation method and application |
| CN108360066B (en) * | 2018-02-07 | 2020-10-02 | 同济大学 | Infrared nonlinear optical crystal mixed halogen potassium bismuthate and preparation method and application thereof |
| CN109338471A (en) * | 2018-11-28 | 2019-02-15 | 同济大学 | A kind of mid-infrared light frequency-doubling crystal fluoro tungsten Potassiumiodate material and preparation and application |
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| CN104962992B (en) | 2017-06-27 |
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