CN100443641C - Second-order non-linear optical crystal material and its synthesis process and use - Google Patents
Second-order non-linear optical crystal material and its synthesis process and use Download PDFInfo
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- CN100443641C CN100443641C CNB2006100192666A CN200610019266A CN100443641C CN 100443641 C CN100443641 C CN 100443641C CN B2006100192666 A CNB2006100192666 A CN B2006100192666A CN 200610019266 A CN200610019266 A CN 200610019266A CN 100443641 C CN100443641 C CN 100443641C
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Abstract
The present invention discloses one kind of second-order non-linear optical crystal material and its preparation process and use. The crystal material has molecular expression of KLiBeF4 and crystal space group of P63. Its preparation process includes the following steps: setting lithium hydroxide, potassium hydroxide, beryllium fluoride and ammonium hydrofluorate into reactor, adding distilled water, adding hydrofluoric acid while stirring to regulate pH value to 5-7; sealing, heating to 140-160 deg.c and maintaining for over 20hr; lowering the temperature to room temperature and filtering to obtain colorless transparent crystal; and washing with distilled water and vacuum drying to obtain the second-order non-linear optical crystal. The second-order non-linear optical crystal has great transparent windows in deep violet area, visible light area and infrared area, great second-order non-linear optical coefficient, high heat stability, simple synthesis and other advantages.
Description
Technical field
The present invention relates to a kind of second-order non-linear optical crystal material, belong to domain of inorganic chemistry, also belong to the optical material field.
Background technology
Non-linear optical effect originates from the interaction of laser and medium.When in laser has the medium of non-zero second order susceptibility, propagating, can produce non-linear optical effects such as frequency multiplication and frequency, difference frequency, parameter amplification.Along with the continuous development of laser science and technology, aspect frequency inverted, the effect that inorganic nonlinear optical crystal material play more and more is important.Be used for inorganic nonlinear optical material existing BBO (beta-barium metaborate), the LBO (lithium tetraborate) etc. of ultraviolet region at present, and it is still blank at present to can be used for the good non-linear optic crystal of deep ultraviolet (＜200 nanometer) frequency multiplication ripple output.And deep ultraviolet laser has important use to be worth at aspects such as improving the optical information storage density, particularly the deep ultraviolet laser light source below 200 nanometers is in laser chemistry, laser medicine, (wavelength is short more for molecular biology and optical storage, then storage density is big more) etc. the field very wide application prospect is arranged, particularly solidify deep ultraviolet lasers entirely and might replace excimer laser effectively, be used to obtain wavelength and become one of main direction of non-linear optic crystal research less than the frequency-doubling crystal of the deep ultraviolet laser (claiming vacuum ultraviolet (VUV) LASER again) of 200 nanometers so explore.
Summary of the invention:
Problem to be solved by this invention provides a kind ofly to be had bigger Clock Multiplier Factor, high bandwidth and laser damage threshold, have the transparency range of broad and can be used for the synthetic method of the second-order non-linear optical crystal material of deep ultraviolet.
Technical scheme provided by the invention is: second-order non-linear optical crystal material, its molecular formula are KLiBeF
4, the crystal space group is P63.
The frequency-doubled effect of above-mentioned crystalline material is 1.0 * KDP; The scope of seeing through is the 0.13-10 micron; Decomposition temperature is 896 degrees centigrade.
The preparation method of above-mentioned second-order non-linear optical crystal material: lithium hydroxide, potassium hydroxide, beryllium fluoride and etching acid ammonium are inserted in the reactor, add distilled water, stir adding hydrofluoric acid down, regulate the pH value to 5-7; Sealing is heated to 140 ~ 160 degrees centigrade, and keeps constant temperature more than 20 hours; Reduce to room temperature, filter, obtain water white crystal; Gained crystal distilled water wash, vacuum-drying obtains second-order non-linear optical crystal.
The consumption mol ratio of above-mentioned lithium hydroxide, potassium hydroxide, beryllium fluoride and etching acid ammonium is 1: 1: 1: 1～3.
Below be the reaction equation of preparation compound of the present invention:
Inorganic nonlinear optical material KLiBeF disclosed in this invention
4Be to choose [BeF
4] group is as the distortion group, the spatial network that forms by F-K-F to be reaching orderly arrangement, thereby shows bigger macro non-linear optical effect.This compound has the very big window that sees through in the near-infrared region, transparency range reaches 10 microns; Then transparent fully at visible region, the ultraviolet absorption edge observed value reaches 0.13 micron.Have higher non-linearity optical coefficient and other physical properties preferably, can be used as nonlinear optical material and in optical field, be applied.
This class novel inorganic infrared nonlinear optical crystal material that the present invention makes has following characteristics:
1. have bigger frequency-doubled effect (SH gram), Kurtz powder frequency multiplication test result shows that its powder frequency-doubled effect is 1.0 times of KDP;
2. compound has the very wide scope that sees through in ultraviolet, visible region and near-infrared region, and seeing through the interval fully is the 0.13-10 micron;
3. do not contain crystal water, air, water are stablized, not deliquescence, non-efflorescing cementitious;
4. Heat stability is good is lower than 896 degrees centigrade and does not decompose;
5. synthetic method of the present invention is the monocrystalline of synthetic materials directly.
Description of drawings
Fig. 1 is KLiBeF of the present invention
4Structure cell figure;
Fig. 2 is KLiBeF of the present invention
4Accumulation graph;
Fig. 3 is KLiBeF of the present invention
4At ultraviolet-visible-near-infrared absorption spectrum;
Fig. 4 is the infrared permeation spectrum of KLiBeF4 of the present invention; IR (2.5～25 microns) spectrum,
*Be KBr planar water absorption peak;
Fig. 5 is KLiBeF of the present invention
4The thermal weight loss collection of illustrative plates.
Embodiment
Below in conjunction with specific embodiment technical scheme of the present invention is further described:
Embodiment 1:KLiBeF
4The preparation of monocrystalline
0.96 gram lithium hydroxide (40 mmole), 2.24 gram potassium hydroxide (40 mmole), 1.88 gram beryllium fluorides (40 mmole) and 2.20 gram etching acid ammoniums (40 mmole) are inserted in the tetrafluoroethylene reactor (about 20 milliliters of volume), add 10 ml distilled waters, under agitation, add hydrofluoric acid, regulate pH value to 6.Sealing is heated to 140 degrees centigrade, and keeps constant temperature 25 hours.Naturally reduce to room temperature, filter, obtain a large amount of water white crystal.Product distilled water repetitive scrubbing, vacuum-drying directly gets water white transparency KLiBeF
4Monocrystalline.
Embodiment 2:KLiBeF
4The preparation of monocrystalline
0.96 gram lithium hydroxide (40 mmole), 2.24 gram potassium hydroxide (40 mmole), 1.88 gram beryllium fluorides (40 mmole) and 4.40 gram etching acid ammoniums (80 mmole) are inserted in the tetrafluoroethylene reactor (about 20 milliliters of volume), add 14 ml distilled waters, under agitation, add hydrofluoric acid, regulate pH value to 7.Sealing is heated to 150 degrees centigrade, and keeps constant temperature 30 hours.Naturally reduce to room temperature, filter, obtain a large amount of water white crystal.Product distilled water repetitive scrubbing, vacuum-drying directly gets water white transparency KLiBeF
4Monocrystalline.
Embodiment 3:KLiBeF
4The preparation of monocrystalline
0.96 gram lithium hydroxide (40 mmole), 2.24 gram potassium hydroxide (40 mmole), 1.88 gram beryllium fluorides (40 mmole) and 6.60 gram etching acid ammoniums (120 mmole) are inserted in the tetrafluoroethylene reactor (about 20 milliliters of volume), add 16 ml distilled waters, under agitation, add hydrofluoric acid, regulate pH value to 5.Sealing is heated to 160 degrees centigrade, and keeps constant temperature 20 hours.Naturally reduce to room temperature, filter, obtain a large amount of water white crystal.Product distilled water repetitive scrubbing, vacuum-drying directly gets water white transparency KLiBeF
4Monocrystalline.
Embodiment 4:KLiBeF
4The powder frequency-doubled effect
The second-order non-linear optical crystal of preparation is placed on the laser optical path, make a branch of red laser (wavelength is 1064 nanometers) inject sample then, sample produces green light (wavelength is 532 nanometers), and the light wavelength that is produced is the twice of laser wavelength of incidence just.
The gained compound is measured through x-ray crystal structure, and its structure cell figure and crystal structure arrangement are seen accompanying drawing 1 and Fig. 2.The crystalline unit cell parameters is:
α=90 °, β=90 °, γ=120 °;
The anionic group of this kind compound as we can see from the figure: [BeF4] is tetrahedral configuration, and forms reticulated structure by the Li-F-Be key.Bond distance's analysis revealed, four Be-F bond distances are divided into two groups in the tetrahedron: 1.540 Hes
Differ about
And distored direction basically identical, thereby help the geometric superposition of microcosmic second order nonlinear optical effect.Product is through infrared spectra, ultraviolet-visible-near-infrared spectrum, and the heat analysis, sees Fig. 3,4 and 5.Without any absorption, the infrared absorption limit reaches 10 microns to material in part deep UV (ultraviolet light) district, ultraviolet, visible region, has big transparency range; As seen from Figure 4, material just begins weightlessness later at 896 degrees centigrade, has good thermostability.
Claims (1)
1. the preparation method of second-order non-linear optical crystal is characterized in that: lithium hydroxide, potassium hydroxide, beryllium fluoride and etching acid ammonium are inserted in the reactor, add distilled water, stir adding hydrofluoric acid down, regulate the pH value to 5-7; Sealing is heated to 140～160 degrees centigrade, and keeps constant temperature more than 20 hours; Reduce to room temperature, filter, obtain water white crystal; Gained crystal distilled water wash, vacuum-drying obtains second-order non-linear optical crystal; The mol ratio of above-mentioned lithium hydroxide, potassium hydroxide, beryllium fluoride and etching acid ammonium is 1: 1: 1: 1～3.
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| CN104962992B (en) * | 2015-05-25 | 2017-06-27 | 武汉大学 | A kind of middle infrared nonlinear optical crystal material KBi4F13And its preparation method and application |
| CN105002558B (en) * | 2015-06-16 | 2017-12-26 | 武汉大学 | Second-order non-linear optical crystal K2SbF2Cl3And its preparation method and application |
| CN105350081A (en) * | 2015-11-14 | 2016-02-24 | 中国科学院新疆理化技术研究所 | Preparation method and use of potassium lithium sulfate nonlinear optical crystal |
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Non-Patent Citations (6)
| Title |
|---|
| Structure des Orthofluoroberyllates de Lithium MLiBeF4. Par J. Le Roy等.Acta Cryst.,Vol.B28 . 1972 |
| Structure des Orthofluoroberyllates de Lithium MLiBeF4. Par J. Le Roy等.Acta Cryst.,Vol.B28 . 1972 * |
| 无机硼酸盐体系的二阶非线性光学晶体材料. 程文旦等.结构化学，第16卷第2期. 1997 |
| 无机硼酸盐体系的二阶非线性光学晶体材料. 程文旦等.结构化学，第16卷第2期. 1997 * |
| 无机纳米粒子的二阶光学非线性研究进展. 张宇等.无机化学学报，第18卷第12期. 2002 |
| 无机纳米粒子的二阶光学非线性研究进展. 张宇等.无机化学学报，第18卷第12期. 2002 * |
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