CN1834310A - Method of preparing second-order non-linear optical materials, and uses thereof - Google Patents
Method of preparing second-order non-linear optical materials, and uses thereof Download PDFInfo
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- CN1834310A CN1834310A CNA2006100184566A CN200610018456A CN1834310A CN 1834310 A CN1834310 A CN 1834310A CN A2006100184566 A CNA2006100184566 A CN A2006100184566A CN 200610018456 A CN200610018456 A CN 200610018456A CN 1834310 A CN1834310 A CN 1834310A
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Abstract
This invention discloses a method for preparing a second-order nonlinear optical crystalline material, which comprises the steps of: mixing iodoform, sulfur powder and solvent carbon bisulfide in an airtight reactor, reacting at 60-80 deg.C for 20-35 h to obtain a solution of the second-order nonlinear optical crystalline material in carbon bisulfide, adding the solution into a glass container, and placing the glass container in a constant temperature cabinet for a certain time to obtain orange bulk single crystals. The method has such advantages as short reaction time, moderate experimental conditions, high product purity and simple operation. The crystalline material can be widely applied in optical field.
Description
Technical field
The invention belongs to domain of inorganic chemistry, also belong to material science and optical field, it relates to a kind of preparation method of inorganic second-order non-linear optical crystal material, also relates to the application of this crystalline material aspect THz wave simultaneously.
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, parameter amplification.THz wave is normally defined frequency from 0.1-10 Terahertz (10
12s
-1) hertzian wave in scope.The central section of research is mainly within the scope of 0.3～3 Terahertz now.Be very much the transliteration of billion (Tera), so terahertz electromagnetic wave is also referred to as T ray, it belongs to far infrared and sub-millimeter wave category.Because it is clipped between microwave and infrared rays, technically in the middle of traditional microwave technology and optical technology, to such an extent as to the research of long-time rare this respect forms Terahertz clear area (Jia Gang, Wang Li, Zhang Xicheng, Chinese science fund 2002,200).Terahertz is in all many-sided application, as the property research of semiconductor material, high temperature superconducting materia, tomography technology, unmarked genetic test, the imaging of cell levels, particularly anti-terrorism aspect is to chemistry and biological detection etc., and the importance of Terahertz having been studied shows especially out.Lacking superpower, low cost and portable room temperature Terahertz light source is the main factor of the modern THz wave application of restriction.
There is several different methods can obtain tera-hertz spectra, wherein just comprised the second order nonlinear optical effect that utilizes crystal.As to utilize optical rectification be a kind of common methods that produces broadband laser pulse Terahertz, it is the inverse process (M.Bass, P.A.Frank, J.F.Ward, et al., Phys.Rev.Lett., 1991,9,446) based on electrooptic effect.From 20 century 70s, scientist starts to adopt two kinds of laser to carry out nonlinear optics mixing to produce THz wave, Basic practice is to have the continuous wavelength laser of minute differences to incide in same second nonlinear non-linear optic crystal two bundle frequencies, by producing by the hunting of frequency with frequently and centered by difference frequency, utilize difference frequency can produce THz wave (B.Ferguson, Zhang Xicheng, physics, 2003,32 (5), 286).At present, traditional semi-conductor nonlinear optical material GaAs and ZnTe and organic nonlinear optical crystal material DAST etc. have started transmitting (X.C.Zhang, the Y.Jin for THz wave, K.Yang, er al., Phys.Rev.Lett., 1992,69,2303; A.Rice, et al., Phys.Lett., 1994,, 1324.c) X.C.Zhang, et al., Appl.Phys.Lett., 1991,61,3080).
(CHI
3) (S
8)
3there is large nonlinear optical coefficients (A.Saoc, M.Samoc, D.Kohler, M.Stahelin, J.Funfschilling, I.Zschokke-Granacher, Mol.Cryst.Liq.Cryst.Sci.Technol., Sect.B:Nonl.Opt.2 (1992) 13).As far as we know, document in the past [T, Bjorvatten, O.Hassel, A.Linaheim, Acta Chem.Scand., 1963,17:689,10; Samoc A, Samoc M, Prasad PN, J.Opt.Soc.Am., 1992,9:1819] preparation method that adopts is at CHI
3cS
2in solution, add greatly excessive S powder, by naturally volatilizing to obtain the crystallite of product.Because sulphur is at CS
2in solubleness very low, therefore reaction is mainly carried out on the interface of solid-liquid two-phase, the product obtaining is often mingled with a large amount of impurity, is difficult to obtain the product that purity is higher; And due to the habit of material self, the monocrystalline of growth is the [W.S.Fernando of needle-like often, J.Inorg.Nucl.Chem., 1981,43:1141], seriously limit the application of material, also there is no at present the Perfected process about the large size single crystal of this material of growing.
Summary of the invention
The object of the invention is to be to provide a kind of preparation method of second-order non-linear optical crystal material, the method has that the reaction times is short, experiment condition is gentle, product purity is high, simple to operate.
Another object of the present invention is to provide the application of second-order non-linear optical crystal material in Terahertz.
For achieving the above object, the present invention adopts following technical scheme, plays step to be:
A, by iodoform, sulphur powder and dithiocarbonic anhydride in airtight solvent thermal reaction device, by solvent thermal reaction, generate second-order non-linear optical crystal material, reaction formula:
During reaction, the mol ratio of raw material iodoform and sulphur powder is iodoform: sulphur powder=1: 3～4.
B, reaction are in airtight solvent thermal reaction device, and solvent dithiocarbonic anhydride adds to 60%～80% of reactor volume, and temperature of reaction is controlled at 60～80 ℃, through the reaction of 20～35 hours, can obtain the dithiocarbonic anhydride solution of second-order non-linear optical crystal material.
C, the dithiocarbonic anhydride solution of the second-order non-linear optical crystal material making is contained in Glass Containers slot and that be connected with drying tube, then be placed in the thermostatic bath of 10-15 ℃, make slowly volatilization naturally of solvent, through 15-30 days, obtain orange-yellow bulk-shaped monocrystal.
The second nonlinear luminescent crystal material obtaining is placed in the light path that sweep limit is 0.2-2.6 Terahertz, makes the light wave of continuous wavelength inject sample, in whole sweep limit, crystalline material full impregnated mistake, obtains continuously transmission Terahertz light wave;
The present invention has following characteristics:
1. adopt solvent-thermal method to prepare second-order non-linear optical crystal material;
2. preparation method's mild condition, the reaction times is short, and product purity is high, simple to operate;
3. utilize simple solvent evaporation method to grow better, the larger-size bulk-shaped monocrystal of quality from the solution of the product that obtains;
4. do not contain crystal water, to air-stable, not deliquescence, and Heat stability is good, heat decomposition temperature is greater than 250 ℃;
5. crystalline material does not absorb within the scope of 0.2-2.6 Terahertz, Terahertz light wave full impregnated mistake;
Accompanying drawing explanation
Fig. 1 is the molecular structure of second-order non-linear optical crystal material of the present invention;
Fig. 2 is the crystal accumulation figure of second-order non-linear optical crystal material of the present invention;
Gained compound is identified through X-ray single crystal diffraction, has been measured crystalline structure.Its crystalline structure is shown in Fig. 1,2, and resulting result and result by references are basically identical, illustrates that the material that the present invention obtains is target material.As can be seen from Fig. 1, each carbon atom all with 3 iodine atoms around, a hydrogen atom connects, carbon-iodine bond length is consistent, due to the long difference of carbon-iodine and C-H, make [iodoform] tetrahedron become asymmetric tetrahedron, so this group to have large microcosmic non-linear; Each [iodoform] group has 6 sulphur octatomic rings around, and this ring is connected with [iodoform] group by Van der Waals force.As seen from Figure 2, the orientation of [iodoform] group is in full accord, and this is conducive to microcosmic second order nonlinear optical effect and mutually superposes, thereby produces large macroscopical second order nonlinear optical effect.
Fig. 3 is the monocrystalline scanned picture of second-order non-linear optical crystal material of the present invention;
From photo, can see, the monocrystalline that the present invention obtains is faint yellow, bulk.
Fig. 4 is Terahertz (0.1～2.6 Terahertz) spectrum of second-order non-linear optical crystal material of the present invention;
From figure, can see, in whole sweep limit, second-order non-linear optical crystal material does not all have to absorb, and can obtain continuously transmission Terahertz light wave;
Fig. 5 is the thermal weight loss collection of illustrative plates of second-order non-linear optical crystal material of the present invention.
From figure, can see, second-order non-linear optical crystal material has higher thermostability, and below 250 ℃ time, material does not decompose weightlessness.
Embodiment
Below in conjunction with specific embodiment, technical scheme of the present invention is further described:
Embodiment 1:
The preparation of second-order non-linear optical crystal material:
1) 1.5748 grams of iodoform (40 mmole) and 1.066 grams of sulphur powder (0.12 mole) are placed in to the tetrafluoroethylene reactor (approximately 20 milliliters of volumes) with stainless steel outer sleeve, add approximately 12 milliliters of (can be 13,14,15,16 milliliters) dithiocarbonic anhydride, with putting into hydrothermal reactor after stainless steel outer sleeve sealing, in 65 ℃ of (can be 60,62,68,70,72,75,78 and 80 ℃) isothermal reactions 30 hours (can be 20,22,26,28,32,35 hours).Naturally cooling, filters rapidly, and the dithiocarbonic anhydride eluent solvent filter cake with a large amount of, obtains and be in a large number mauve solution, is the dithiocarbonic anhydride solution of second-order non-linear optical crystal material.
2) the dithiocarbonic anhydride solution of the second-order non-linear optical crystal material obtaining is contained in round-bottomed flask (can be the containers such as Florence flask, Erlenmeyer flask), bottleneck connects a drying tube, then be placed in 10 ℃ of (can be 11,12,13,14,15 ℃) Water Tanks with Temp.-controlled, static, allow solvent slowly naturally volatilize, through about 20 days, grow up to the transparent faint yellow monocrystalline of bulk of large-size.
Embodiment 2:
The preparation of second-order non-linear optical crystal material:
1) 1.5748 grams of iodoform (40 mmole) and 1.244 grams of sulphur powder (0.14 mole) are placed in to the tetrafluoroethylene reactor (approximately 20 milliliters of volumes) with stainless steel outer sleeve, add approximately 12 milliliters of (can be 13,14,15,16 milliliters) dithiocarbonic anhydride, with putting into hydrothermal reactor after stainless steel outer sleeve sealing, in 65 ℃ of (can be 60,62,68,70,72,75,78 and 80 ℃) isothermal reactions 30 hours (can be 20,22,26,28,32,35 hours).Naturally cooling, filters rapidly, and the dithiocarbonic anhydride eluent solvent filter cake with a large amount of, obtains and be in a large number mauve solution, is the dithiocarbonic anhydride solution of second-order non-linear optical crystal material.
2) the dithiocarbonic anhydride solution of the second-order non-linear optical crystal material obtaining is contained in round-bottomed flask (can be the containers such as Florence flask, Erlenmeyer flask), bottleneck connects a drying tube, then be placed in 10 ℃ of (can be 11,12,13,14,15 ℃) Water Tanks with Temp.-controlled, static, allow solvent slowly naturally volatilize, through about 20 days, grow up to the transparent faint yellow monocrystalline of bulk of large-size.
Embodiment 3:
The preparation of second-order non-linear optical crystal material:
1) 1.5748 grams of iodoform (40 Bo mole) and 1.421 grams of sulphur powder (0.16 mole) are placed in to the tetrafluoroethylene reactor (approximately 20 milliliters of volumes) with stainless steel outer sleeve, add approximately 12 milliliters of (can be 13,14,15,16 milliliters) dithiocarbonic anhydride, with putting into hydrothermal reactor after stainless steel outer sleeve sealing, in 65 ℃ of (can be 60,62,68,70,72,75,78 and 80 ℃) isothermal reactions 30 hours (can be 20,22,26,28,32,35 hours).Naturally cooling, filters rapidly, and the dithiocarbonic anhydride eluent solvent filter cake with a large amount of, obtains and be in a large number mauve solution, is the dithiocarbonic anhydride solution of second-order non-linear optical crystal material.
2) the dithiocarbonic anhydride solution of the second-order non-linear optical crystal material obtaining is contained in round-bottomed flask (can be the containers such as Florence flask, Erlenmeyer flask), bottleneck connects a drying tube, then be placed in 10 ℃ of (can be 11,12,13,14,15 ℃) Water Tanks with Temp.-controlled, static, allow solvent slowly naturally volatilize, through about 20 days, grow up to the transparent faint yellow monocrystalline of bulk of large-size.
Embodiment 4:
The Terahertz wave spectrum of second-order non-linear optical crystal material:
1) second-order non-linear optical crystal of preparation is placed on laser optical path, then make a branch of red laser (wavelength is 1064 nanometers) inject sample, sample produces green light (wavelength is 532 nanometers), and the light wavelength producing is the twice of laser wavelength of incidence just;
2) crystalline material obtaining and polyethylene are mixed and milled evenly according to the ratio of 1: 6, be pressed into 12 millimeters of diameters, thickness is the thin slice of 1.0 millimeters, is placed in terahertz light light path, and sweep limit is 0.1-2.6 Terahertz.Make the light wave of continuous wavelength inject sample, in whole sweep limit, crystalline material full impregnated mistake, obtains continuously transmission Terahertz light wave; The signal obtaining is collected by computer, after Fourier transform, obtains the Terahertz wave spectrum of material.
Embodiment 5:
The Terahertz wave spectrum of second-order non-linear optical crystal material:
1) second-order non-linear optical crystal material of preparation is milled into about 200 object powder, then being contained in two sides has in the sample pool of glass port, afterwards sample pool is placed on laser optical path, make a branch of red laser (wavelength is 1064 nanometers) inject sample pool, produce green light (wavelength is 532 nanometers), the light wavelength producing is the twice of laser wavelength of incidence just;
2) crystalline material obtaining and polyethylene are mixed and milled evenly according to the ratio of 1: 5, be pressed into 12 millimeters of diameters, thickness is the thin slice of 1.0 millimeters, is placed in terahertz light light path, and sweep limit is 0.1-2.6 Terahertz.Make the light wave of continuous wavelength inject sample, in whole sweep limit, crystalline material full impregnated mistake, obtains continuously transmission Terahertz light wave; The signal obtaining is collected by computer, after Fourier transform, obtains the Terahertz wave spectrum of material.
Claims (3)
1. a preparation method for second-order non-linear optical crystal material, it comprises the following steps:
A) by iodoform, sulphur powder and dithiocarbonic anhydride, by solvent thermal reaction, generate, reaction formula is as follows:
B) reaction is in airtight solvent thermal reaction device, solvent dithiocarbonic anhydride adds to 60%～80% of reactor volume, temperature of reaction is controlled at 60～80 ℃, through the reaction of 20～35 hours, can make the dithiocarbonic anhydride solution of second-order non-linear optical crystal material;
C) the dithiocarbonic anhydride solution of the second-order non-linear optical crystal material making is contained in Glass Containers slot and that be connected with drying tube, is then placed in the thermostatic bath of 10-15 ℃, make solvent evaporates, through 15-30 days, obtain orange-yellow bulk-shaped monocrystal.
2. the preparation method of a kind of second-order non-linear optical crystal material according to claim 1, is characterized in that: the mol ratio of iodoform and sulphur powder is 1: 3～4.
3. the application of a kind of second-order non-linear optical crystal material claimed in claim 1 in THz wave.
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101216656B (en) * | 2008-01-14 | 2010-06-23 | 武汉大学 | Inorganic infrared nonlinear optical crystal material and method for making same and uses |
| CN101831699A (en) * | 2009-03-13 | 2010-09-15 | 中国科学院福建物质结构研究所 | Non-linear optical crystal of iodic acid barium niobate |
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| CN1696357A (en) * | 2005-03-24 | 2005-11-16 | 武汉大学 | Sb13 (S8)3 crystalline material, preparation method and application |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101216656B (en) * | 2008-01-14 | 2010-06-23 | 武汉大学 | Inorganic infrared nonlinear optical crystal material and method for making same and uses |
| CN101831699A (en) * | 2009-03-13 | 2010-09-15 | 中国科学院福建物质结构研究所 | Non-linear optical crystal of iodic acid barium niobate |
| CN101831699B (en) * | 2009-03-13 | 2014-03-05 | 中国科学院福建物质结构研究所 | Non-linear optical crystal of iodic acid barium niobate |
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