CN1699640A - Nonlinear optical crystal and preparation method thereof - Google Patents
Nonlinear optical crystal and preparation method thereof Download PDFInfo
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- CN1699640A CN1699640A CN 200510049508 CN200510049508A CN1699640A CN 1699640 A CN1699640 A CN 1699640A CN 200510049508 CN200510049508 CN 200510049508 CN 200510049508 A CN200510049508 A CN 200510049508A CN 1699640 A CN1699640 A CN 1699640A
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Abstract
The present invention discloses a kind of nonlinear optical crystal and its preparation method. Making use of coordinate bonding effect between metal and organic ligand, nonlinear optical crystal material zinc succinate [Zn(C4H4O4)] is obtained, belonging to monoclinic system. The molecular formula is Zn(C4H4O4),space group is C2,crystal cell parameters a = 7.585 A , b=5.984 A, c=6.253 A, alpha= gamma =90 degree, beta= 108.45 degree, and crystal cell volume V=269.1 A3, Z=2. Frequency multiplier coefficient of Zn(C4H4O4) crystal was measured with binary channel second harmonics analyzer. Result shows that effective frequency multiplier coefficient of Zn(C4H4O4) crystal is 6.5 times of that of KDP crystal d36, and phase match can be realized.
Description
Technical Field
The invention relates to an optical crystal, in particular to a nonlinear optical crystal and a preparation method thereof.
Background
The nonlinear optical crystal material is used as an electronic information material which is extremely important in the photoelectron industry, changes the wavelength of laser through nonlinear optical processes such as frequency multiplication, sum frequency, difference frequency, frequency mixing, optical parametric oscillation and the like to obtain laser sources in different wavelength ranges, and can realize laser signal processing in various forms, so that the nonlinear optical crystal material is widely applied to the technical fields of emerging laser and photoelectron, such as the technical fields of optical fiber communication, optical storage, laser processing, laser medical treatment, laser weapons, laser nuclear fusion and the like. In practical applications, it is required that the nonlinear optical crystal should have as high laser frequency doubling efficiency as possible, be easy to implement phase matching, and have a high laser damage threshold and stable physicochemical properties.
Among the nonlinear optical crystals, those that have been first practically obtained are inorganic nonlinear optical crystals such as low-temperature phase barium metaborate (b-BBO), lithium triborate (LBO), potassium titanyl phosphate (KTP), potassium dihydrogen phosphate (KDP), Lithium Niobate (LN), and the like. However, the inorganic nonlinear optical crystals are of a few kinds and are difficult to meet the special requirements of various applications. In the last two decades, the research on organic nonlinear optical crystals has attracted people's attention and has been greatly developed, but the laser damage threshold is generally low, and many crystals absorb in the frequency doubling band, so that the nonlinear optical effect is reduced or even completely disappears. So that the organic nonlinear optical crystal cannot be put into practical use until now.
The rapid development of coordination chemistry provides a new idea for the design and development of novel functional materials and greatly promotes the development of material science.
Disclosure of Invention
The technical problem to be solved by the present invention is to provide a nonlinear optical crystal with strong nonlinear optical frequency doubling effect and suitable for practical use and a preparation method thereof.
The technical scheme adopted by the invention for solving the technical problems is as follows: a non-linear optical crystal is a zinc succinate crystal belonging to monoclinic system and its molecular formula is Zn (C)4H4O4) The space group is C2, the unit cell parameter is a-7.585 Å, b-5.984 Å, C-6.253 Å - γ -90 °, β -108.45 °, and the unit cell volume is V-269.1 Å3，Z＝2。
A process for preparing the non-linear optical crystal includes such steps as ①ZnCl is weighed according to the molar ratio of 1: 12、Na2CO3Respectively dissolving them in secondary distilled water to obtain solutions, ② adding Na2CO3Dropwise addition of the solution to ZnCl2In the solution, ZnCO is obtained through precipitation, separation and washing3③ mixing prepared succinic acid (C) according to the molar ratio of 1: 14H6O4) Dropwise addition of the solution to ZnCO3In the reaction, zinc succinate [ Zn (C) is obtained4H4O4)]④ growing crystal by low-temperature water solution method, and mixing zinc succinate [ Zn (C)4H4O4)]Placing the solution in a growth cylinder, adding zinc succinate seed crystal at a temperature higher than the saturation point by 2 deg.C, cooling to the saturation point, holding the temperature for 24 hr, ⑤ setting the initial growth temperature at 40-50 deg.C, cooling rate at 0.2-0.5 deg.C/day, crystal rotation speed at 10-15 r/min, rotatingThe period is as follows: 30 minutes forward rotation, 10 minutes stop rotation, 30 minutes reverse rotation and 10 minutes stop rotation, and zinc succinate crystals are obtained by growth. In order to improve the stability of the crystal growth temperature field, the crystal growth is preferably carried out by using a water bath double-layer growth cylinder, and distilled water is filled between the outer layer growth cylinder and the inner layer growth cylinder.
Compared with the prior art, the invention has the advantages that the nonlinear optical crystal material zinc succinate [ Zn (C) ] is obtained by means of the coordination bonding effect between metal-organic ligands4H4O4)]Measuring the zinc succinate [ Zn (C) by dual-channel second harmonic analyzer4H4O4)]The frequency doubling coefficient of the crystal shows that: zinc succinate crystal with effective frequency doubling coefficient KDP crystal d366.5 times of the phase matching can be realized; the thermal properties of the crystal are measured by a differential heat and thermogravimetric method, and the results show that: the crystals decomposed at 500 ℃ without phase transition below 500 ℃. Zinc succinate [ Zn (C) of the present invention4H4O4)]The crystal can be widely applied to emerging laser and photoelectron industries, such as optical fiber communication, optical storage, laser processing, laser medical treatment, laser weapons, laser nuclear fusion and other technical fields for manufacturing various optical elements by frequency multiplication, sum frequency, difference frequency, frequency mixing and optical parametric oscillationAnd the nonlinear optical process is used for changing the wavelength of the laser to obtain laser light sources in different wavelength ranges, so that various forms of laser signal processing are realized. The growth parameters and the periodic forward rotation and reverse rotation method set by the invention can ensure that the grown crystal has good optical uniformity; the stability of a crystal growth temperature field can be effectively improved by using the water bath double-layer growth cylinder.
Drawings
FIG. 1 is a schematic structural view of a water bath double-layer growth cylinder for growing crystals according to the present invention;
FIG. 2 shows zinc succinate [ Zn (C) ] of the present invention4H4O4)]A crystal structure;
FIG. 3 shows zinc succinate [ Zn (C) ] of the present invention4H4O4)]Differential thermal and thermogravimetric analysis of crystals.
In FIG. 1, 1 is a liquid seal, 2 is a thermocouple, 3 is a heater, 4 is an outer layer growth cylinder, 5 is an inner layer growth cylinder, 6 is a stirrer, 7 is a crystal, 8 is a space for containing distilled water, 9 is zinc succinate [ Zn (C)4H4O4)]And (3) solution.
Detailed Description
The invention is described in further detail below with reference to the accompanying examples.
EXAMPLE one method for preparing a nonlinear optical crystal comprises ① weighing ZnCl at room temperature in a molar ratio of 1: 12、Na2CO3Respectively dissolving them in secondary distilled water to obtain solutions, ② adding Na2CO3Dropwise addition of the solution to ZnCl2In the solution, ZnCO is obtained through precipitation, separation and washing 3③ mixing prepared succinic acid (C) according to the molar ratio of 1: 14H6O4) Dropwise addition of the solution to ZnCO3In the reaction, zinc succinate [ Zn (C) is obtained4H4O4)]④ growing crystal by low-temperature water solution method, and mixing zinc succinate [ Zn (C)4H4O4)]Putting the solution in an inner layer growth cylinder of a water bath double-layer growth cylinder, filling distilled water between the outer layer growth cylinder and the inner layer growth cylinder, putting zinc succinate seed crystals at a temperature higher than the saturation point by more than 2 ℃, reducing the temperature to the saturation point, keeping the temperature for 24 hours, ⑤ setting the initial growth temperature at 45 ℃, the cooling rate at 0.35 ℃/day, the crystal rotation speed at 12 revolutions per minute, the rotation period at 30 minutes forward rotation, 10 minutes stop rotation, 30 minutes reverse rotation and 10 minutes stop rotation, and growing to obtain zinc succinate crystals with the molecular formula of Zn (C)4H4O4) The zinc succinate crystal belongs to a noncentrosymmetric structure, diffraction data of the zinc succinate crystal are collected on a four-circle diffractometer, and structural analysis shows that the zinc succinate crystal belongs to a monoclinic system, the space group is C2, the unit cell parameters are a-7.585 Å, b-5.984 Å, C-6.253 Å -gamma-90 degrees, β -108.45 degrees and the unit cell volume is V-269.1 Å degrees3And Z is 2. Measuring the zinc succinate [ Zn (C) grown by a double-channel second harmonic analyzer4H4O4)]The frequency doubling coefficient of the crystal shows that: zinc succinate crystal with effective frequency doubling coefficient KDP crystal d366.5 times and is phase-matched. The thermal properties of the crystal are measured by a differential thermal and thermogravimetric method, and the results show that: the crystals decomposed at 500 ℃ without phase transition below 500 ℃.
EXAMPLE two A method for producing a nonlinear optical crystal, which comprises the step of ① in a molar ratio of 1: 1 at room temperatureWell weighed ZnCl2、Na2CO3Respectively dissolving them in secondary distilled water to obtain solutions, ② adding Na2CO3Dropwise addition of the solution to ZnCl2In the solution, ZnCO is obtained through precipitation, separation and washing3③ mixing prepared succinic acid (C) according to the molar ratio of 1: 14H4O4) Dropwise addition of the solution to ZnCO3In the reaction, zinc succinate [ Zn (C) is obtained4H4O4)]④ growing crystal by low-temperature water solution method, and mixing zinc succinate [ Zn (C)4H4O4)]The solution is placed in an inner layer growth jar of a water bath double-layer growth jar, and distilled water is filled between the outer layer growth jar and the inner layer growth jar and is higher than the inner layer growth jarAdding zinc succinate seed crystal at saturation point temperature above 2 deg.C, cooling to saturation point temperature, holding the temperature for 24 hr, ⑤ setting growth start temperature at 40 deg.C, cooling rate at 0.2 deg.C/day, crystal rotation speed at 10 rpm, rotation period of 30 min forward rotation, 10 min stop rotation, 30 min reverse rotation, and 10 min stop rotation to obtain zinc succinate crystal with molecular formula of Zn (C)4H4O4) The zinc succinate crystal belongs to a noncentrosymmetric structure, diffraction data of the zinc succinate crystal are collected on a four-circle diffractometer, and structural analysis shows that the zinc succinate crystal belongs to a monoclinic system, the space group is C2, the unit cell parameters are a-7.585 Å, b-5.984 Å, C-6.253 Å -gamma-90 degrees, β -108.45 degrees and the unit cell volume is V-269.1 Å degrees3And Z is 2. Measuring the zinc succinate [ Zn (C) grown by a double-channel second harmonic analyzer4H4O4)]The frequency doubling coefficient of the crystal shows that: zinc succinate crystal with effective frequency doubling coefficient KDP crystal d366.5 times and is phase-matched. The thermal properties of the crystal are measured by a differential thermal and thermogravimetric method, and the results show that: the crystals decomposed at 500 ℃ without phase transition below 500 ℃.
EXAMPLE III A method for preparing a nonlinear optical crystal, which comprises ① weighing ZnCl at room temperature in a molar ratio of 1: 12、Na2CO3Respectively dissolving them in secondary distilled water to obtain solutions, ② adding Na2CO3Dropwise addition of the solution to ZnCl2In the solution, ZnCO is obtained through precipitation, separation and washing3③ mixing prepared succinic acid (C) according to the molar ratio of 1: 14H4O4) Dropwise addition of the solution to ZnCO3In the reaction, zinc succinate [ Zn (C) is obtained4H4O4)]④ growing crystal by low-temperature water solution method, and mixing zinc succinate [ Zn (C)4H4O4)]Placing the solution in an inner growth cylinder of a water bath double-layer growth cylinder, filling distilled water between the outer growth cylinder and the inner growth cylinder, adding zinc succinate seed crystal at a temperature higher than the saturation point by 2 deg.C, cooling to the saturation point, holding the temperature for 24 hr, ⑤ setting the initial growth temperature at 50 deg.C and the cooling rate at 0.5 deg.CThe crystal rotation speed is 15 r/min, the rotation period is as follows: 30 minutes forward rotation, 10 minutes stop rotation, 30 minutes reverse rotation, 10 minutes stop rotation, zinc succinate crystal is obtained by growth, and the molecular formula of the zinc succinate crystal is Zn (C)4H4O4) The zinc succinate crystal belongs to a noncentrosymmetric structure, diffraction data of the zinc succinate crystal are collected on a four-circle diffractometer, and structural analysis shows that the zinc succinate crystal belongs to a monoclinic system, the space group is C2, the unit cell parameters are a-7.585 Å, b-5.984 Å, C-6.253 Å -gamma-90 degrees, β -108.45 degrees and the unit cell volume is V-269.1 Å degrees3And Z is 2. Measuring the zinc succinate [ Zn (C) grown by a double-channel second harmonic analyzer4H4O4)]The frequency doubling coefficient of the crystal shows that: zinc succinate crystal with effective frequency doubling coefficient KDP crystal d366.5 times and is phase-matched. The thermal properties of the crystal are measured by a differential thermal and thermogravimetric method, and the results show that: the crystals decomposed at 500 ℃ without phase transition below 500 ℃. In the above examples, the purity and the manufacturer of the raw materials used were as follows:
name purity of drug manufacturer
ZnCl299.5% Shanghai refining science and technology institute
Na2CO399.5% Zhejiang province Lanxi City chemical reagent plant
C4H6O499.5% Shanghai chemical agent centralized chemical plant
The chemical reaction of the synthesis is as follows:
Claims (4)
1. a non-linear optical crystal is characterized by that it is a zinc succinate crystal belonging to monoclinic system, and its molecular formula is Zn (C)4H4O4) Space group is C2, unit cell parameter is a 7.585 Å, b 5.984Å, c 6.253 Å ═ γ ═ 90 °, β ═ 108.45 °, unit cell volume V ═ 269.1 Å °3，Z＝2。
2. A process for preparing non-linear optical crystal includes such steps as ① weighing ZnCl at room temp. in the mol ratio of 1: 12、Na2CO3Respectively dissolving them in secondary distilled water to obtain solutions, ② adding Na2CO3Dropwise addition of the solution to ZnCl2In the solution, ZnCO is obtained through precipitation, separation and washing3③ mixing prepared succinic acid (C) according to the molar ratio of 1: 14H6O4) Dropwise addition of the solution to ZnCO3In the reaction, zinc succinate [ Zn (C) is obtained4H4O4)]④ growing crystal by low-temperature water solution method, and mixing zinc succinate [ Zn (C)4H4O4)]Putting the solution in a growth cylinder, putting zinc succinate seed crystals at a temperature higher than the saturation point by more than 2 ℃, reducing the temperature to the saturation point, keeping the temperature for 24 hours, ⑤ setting the initial growth temperature at 40-50 ℃, the cooling rate at 0.2-0.5 ℃/day, the crystal rotation speed at 10-15 r/min, and the rotation period of 30 minutes forward rotation, 10 minutes stop rotation, 30 minutes reverse rotation and 10 minutes stop rotation, and growing to obtain the zinc succinate crystal.
3. The method for growing a nonlinear optical crystal as claimed in claim 2, wherein the crystal is grown using a water bath double layer growth tank, and distilled water is filled between the outer layer growth tank and the inner layer growth tank.
4. The method according to claim 2, wherein the initial temperature of the crystal growth is set to 45 ℃, the cooling rate is 0.35 ℃/day, and the crystal rotation speed is 12 rpm.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN100507093C (en) * | 2006-07-28 | 2009-07-01 | 中国科学院理化技术研究所 | Fluxing agent growth method of calcium fluoborate nonlinear optical crystal |
| CN101575735B (en) * | 2009-05-11 | 2011-08-31 | 宁波大学 | Pyridine-2,4,6-triformate manganese ferro-electrical functional material and preparation method thereof |
| CN102560651A (en) * | 2010-12-16 | 2012-07-11 | 中国科学院福建物质结构研究所 | Dielectric crystal sodium borate mandelate dihydrate and its preparation method and application |
| CN101560218B (en) * | 2008-04-18 | 2013-03-06 | 中国科学院福建物质结构研究所 | Organometallic complex of nonlinear optical and ferroelectric material, synthesis and application thereof |
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| CN1059196C (en) * | 1997-12-30 | 2000-12-06 | 徐同香 | Prepn. tech. of zinc acetate |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100507093C (en) * | 2006-07-28 | 2009-07-01 | 中国科学院理化技术研究所 | Fluxing agent growth method of calcium fluoborate nonlinear optical crystal |
| CN101560218B (en) * | 2008-04-18 | 2013-03-06 | 中国科学院福建物质结构研究所 | Organometallic complex of nonlinear optical and ferroelectric material, synthesis and application thereof |
| CN101575735B (en) * | 2009-05-11 | 2011-08-31 | 宁波大学 | Pyridine-2,4,6-triformate manganese ferro-electrical functional material and preparation method thereof |
| CN102560651A (en) * | 2010-12-16 | 2012-07-11 | 中国科学院福建物质结构研究所 | Dielectric crystal sodium borate mandelate dihydrate and its preparation method and application |
| CN102560651B (en) * | 2010-12-16 | 2016-06-29 | 中国科学院福建物质结构研究所 | A kind of dielectric crystal two hydration boric acid mandelic acid sodium salt and its production and use |
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