阅读说明：本技术 一种含羟基、甲基的3-异丙基异噁唑酮体系非线性光学晶体及其制法和用途 (3-isopropyl isoxazolone system nonlinear optical crystal containing hydroxyl and methyl, and preparation method and application thereof ) 是由 张馨元 高明校 胡章贵 吴以成 王继扬 于 2019-11-06 设计创作，主要内容包括：一种含羟基、甲基的3-异丙基异噁唑酮体系(C<Sub>15</Sub>H<Sub>17</Sub>NO<Sub>3</Sub>)非线性光学晶体及其制法和用途。本发明提供的C<Sub>15</Sub>H<Sub>17</Sub>NO<Sub>3</Sub>非线性光学晶体,不具有对称中心,属于正交晶系,空间群为Pca2<Sub>1</Sub>(No.29),晶胞参数为：<Image he="59" wi="700" file="DDA0002262492390000011.GIF" imgContent="drawing" imgFormat="GIF" orientation="portrait" inline="no"></Image>α＝γ＝β＝90°,Z＝4,<Image he="63" wi="354" file="DDA0002262492390000012.GIF" imgContent="drawing" imgFormat="GIF" orientation="portrait" inline="no"></Image>本发明还提供了由所述C<Sub>15</Sub>H<Sub>17</Sub>NO<Sub>3</Sub>非线性光学晶体制备的非线性光学器件,所述器件为太赫兹波发生器、二次谐波发生器、上频率转换器、下频率转换器或光参量振荡器。(3-isopropyl isoxazolone system (C) containing hydroxyl and methyl 15 H 17 NO 3 ) Nonlinear optical crystal and its preparation method and application. C provided by the invention 15 H 17 NO 3 The nonlinear optical crystal has no symmetry center, belongs to orthorhombic system, and has space group of Pca2 1 (No.29), unit cell parameters are: α＝γ＝β＝90°，Z＝4, the invention also provides a preparation method of the compound C 15 H 17 NO 3 The nonlinear optical device is prepared from a nonlinear optical crystal, and the device is a terahertz wave generator, a second harmonic generator, an upper frequency converter, a lower frequency converter or an optical parametric oscillator.)

1. A3-isopropyl isoxazolone system nonlinear optical crystal containing hydroxyl and methyl, and its chemical formula is C₁₅H₁₇NO₃The chemical structure is as follows:

characterized in that the crystal does not have a symmetrical center and belongs to an orthorhombic system, and the space group is Pca2₁(No.29), unit cell parameters are:

2. a method for preparing a hydroxyl-and methyl-containing 3-isopropyl isoxazolone system nonlinear optical crystal according to claim 1, which adopts a spontaneous crystallization volatilization method for growth, and comprises the following steps:

(1) at room temperature, adding C₁₅H₁₇NO₃Dissolving a compound in a solvent to obtain a compound solution;

(2) placing the obtained compound solution in a semi-closed container, and obtaining C after the solvent is evaporated₁₅H₁₇NO₃A nonlinear optical crystal.

3. A method for preparing a hydroxy-methyl-containing 3-isopropyl isoxazolone system nonlinear optical crystal according to claim 1, which adopts a spontaneous crystallization cooling method for growth, and comprises the following steps:

at 40-60 ℃, adding C₁₅H₁₇NO₃Preparing a saturated solution from the compound, preserving heat for 10-30 hours, and cooling at a rate of 0.2-5 ℃/day to obtain C₁₅H₁₇NO₃A nonlinear optical crystal.

4. A method for preparing a hydroxyl-methyl-containing 3-isopropyl isoxazolone system nonlinear optical crystal as claimed in claim 1, which adopts a seed crystal method for growth, and comprises the following steps:

(1) at 40-60 ℃, adding C₁₅H₁₇NO₃Preparing a saturated solution from the compound, and adding seed crystals after heat preservation for 10-30 hours;

(2) raising the temperature of the obtained seed crystal solution to 1-10 ℃ above the saturation temperature, preserving heat for 0.5-3 hours, then cooling to the saturation temperature, preserving heat for 10-30 hours, and finally cooling at the rate of 0.1-5 ℃/day to obtain C₁₅H₁₇NO₃A nonlinear optical crystal.

5. The method for preparing 3-isopropyl isoxazolone system nonlinear optical crystal containing hydroxyl and methyl according to claims 2 to 4, characterized in that the solvent is one or a mixture of methanol, ethanol, acetonitrile, acetone, chloroform, 1, 2-dichloroethane, ethyl acetate, diethyl ether, ethylene glycol, dimethyl sulfoxide or dimethylformamide.

6. Use of the hydroxyl group-containing, methyl group-containing 3-isopropyl isoxazolone system nonlinear optical crystal according to claim 1, characterized by being used for producing a nonlinear optical device.

7. Use according to claim 6, wherein said non-linear optical device is capable of passing at least one beam of incident electromagnetic radiation through at least one C₁₅H₁₇NO₃The device for generating at least one beam of output radiation with frequency different from that of incident electromagnetic radiation after the nonlinear optical crystal is a terahertz wave generator, a second harmonic generator, an upper frequency converter, a lower frequency converter or an optical parametric oscillator.

Technical Field

The invention relates to the technical field of nonlinear optical crystals, in particular to a 3-isopropyl isoxazolone system (C) containing hydroxyl and methyl₁₅H₁₇NO₃) Nonlinear optical crystal and its preparation and use.

Background

Nonlinear optics is a branch of modern optics, and mainly researches nonlinear phenomena generated by media under the action of strong coherent light and application of the nonlinear phenomena. The nonlinear optical effect mainly comprises frequency doubling, difference frequency, sum frequency, optical parametric oscillation and the like, and crystals with the nonlinear optical effect are collectively called nonlinear optical crystals. The nonlinear optical crystal can be used for manufacturing various nonlinear optical devices such as harmonic generators, optical parametric amplifiers and the like, and laser frequency conversion is realized through the nonlinear optical devices, so that the wavelength range of the laser is widened, and the laser can be widely applied.

Terahertz (THz) waves generally refer to electromagnetic waves having a frequency range of 0.1 to 10THz (1THz ═ 10 THz)¹²Hz) with a wavelength between that of infrared light and microwaves (30 μm to 3 mm). The band is a transition region of electronics and electron optical technology, and has important effects in the fields of terahertz imaging, space detection, biomedicine, processing, national defense industry and the like. At present, nonlinear optical crystals suitable for being applied to terahertz wave bands mainly include: ZnTe, GaP, DAST, DSTMS, OH1 and the like, but the problems of difficult growth of high-quality single crystals, narrow light transmission range, serious two-photon absorption and the like limit the wide application of the crystals. Therefore, the development of novel terahertz waveband nonlinear optical crystal is the current nonlinear optical crystalOne of the important leading issues in the material field.

According to the survey, C is not available yet₁₅H₁₇NO₃The chemical structure, single crystal structure, crystal growth and second harmonic effect in nonlinear optics of the compound and the application in terahertz wave band are reported.

Disclosure of Invention

The present invention aims to overcome the above-mentioned disadvantages of the prior art and provides C₁₅H₁₇NO₃The nonlinear optical crystal, the preparation method thereof and the manufactured nonlinear optical device expand the variety of the terahertz waveband nonlinear optical crystal.

In order to achieve the above object, the present invention provides the following technical solutions:

3-isopropyl isoxazolone system (C) containing hydroxyl and methyl₁₅H₁₇NO₃) A compound having the chemical structure shown in formula I:

the invention provides a compound C₁₅H₁₇NO₃The nonlinear optical crystal has no symmetry center, belongs to orthorhombic system, and has space group of Pca2₁(No.29), unit cell parameters are:α＝γ＝β＝90°，Z＝4,

the crystal growth method is simple, easy to operate and low in cost; obtained C₁₅H₁₇NO₃The frequency doubling effect intensity of the crystal is 0.5-1 times of OH1, the crystal is stable in physical and chemical properties and does not deliquesce, and the crystal can be used for manufacturing nonlinear optical devices.

The invention also provides the compound C₁₅H₁₇NO₃Three preparation methods of the nonlinear optical crystal,

the first method adopts a spontaneous crystallization volatilization method for growth, and comprises the following steps:

(1) at room temperature, adding the C₁₅H₁₇NO₃Dissolving a compound in a solvent to obtain a compound solution;

(2) placing the obtained compound solution in a semi-closed container, and obtaining C after the solvent is evaporated₁₅H₁₇NO₃A nonlinear optical crystal.

The second method adopts a spontaneous crystallization cooling method for growth, and comprises the following steps:

at 40-60 ℃ (preferably 40-50 ℃, more preferably 50 ℃), adding the C₁₅H₁₇NO₃Preparing a saturated solution from the compound, preserving heat (preferably for 10-30 h, more preferably for 15-20 h), cooling (preferably for 0.2-5 ℃/d, more preferably for 1-2 ℃/d) to obtain C₁₅H₁₇NO₃A nonlinear optical crystal.

The third method adopts a seed crystal method for growth, and comprises the following steps:

(1) at 40-60 ℃ (preferably 40-55 ℃, more preferably 45 ℃), adding the C₁₅H₁₇NO₃Preparing a saturated solution from the compound, preserving the temperature (preferably for 10-30 h, more preferably for 15-20 h), and adding seed crystals;

(2) raising the temperature of the obtained seed crystal-containing solution to 1-10 ℃ above the saturation temperature (preferably raising the temperature to 5 ℃), then preserving the heat (preferably for 0.5-3 h, more preferably for 2h), then reducing the temperature to 1-10 ℃ (preferably reducing the temperature to 5 ℃) to the saturation temperature, preserving the heat (preferably for 10-30 h, more preferably for 15-20 h), and finally reducing the temperature (preferably for 0.1-5 ℃/h, more preferably for 0.1 ℃/h) to obtain C₁₅H₁₇NO₃A nonlinear optical crystal.

In the preparation method of the three crystals, the solvent is one or a mixture of methanol, ethanol, acetonitrile, acetone, chloroform, 1, 2-dichloroethane, ethyl acetate, diethyl ether, ethylene glycol, dimethyl sulfoxide or dimethylformamide.

C provided by the invention₁₅H₁₇NO₃The use of nonlinear optical crystals for the preparation of crystalsA linear optical device; the nonlinear optical device comprises at least one beam of incident electromagnetic radiation passing through at least one block C₁₅H₁₇NO₃Means for generating at least one output radiation having a frequency different from that of the incident electromagnetic radiation after the nonlinear optical crystal.

The device is a terahertz wave generator, a secondary harmonic generator, an upper frequency converter, a lower frequency converter or an optical parametric oscillator.

C can be obtained by the three methods₁₅H₁₇NO₃The non-linear optical crystal can obtain large-size C by prolonging the growth time₁₅H₁₇NO₃A nonlinear optical crystal. According to crystallographic data, C of the invention₁₅H₁₇NO₃And (3) orienting and cutting the nonlinear optical crystal blank, and performing rough grinding and brightening to obtain the nonlinear optical crystal blank serving as a nonlinear optical device.

The invention has the advantages and beneficial effects that:

c provided by the invention₁₅H₁₇NO₃The preparation method of the nonlinear optical crystal is simple and convenient to operate, easy to implement and low in cost. Obtained C₁₅H₁₇NO₃The crystal powder has the frequency doubling effect strength of 0.5-1 time of OH1, and the crystal has stable physical and chemical properties and is not deliquescent and can be used for manufacturing nonlinear optical devices.

Drawings

FIG. 1 shows the present invention C₁₅H₁₇NO₃A crystal structure diagram of the nonlinear optical crystal;

FIG. 2 is a schematic diagram of the working principle of the nonlinear optical device of the present invention;

in the figure: 1-laser, 2-incident beam, 3-C₁₅H₁₇NO₃Nonlinear optical crystal, 4-emergent beam, 5-filtering wave plate.

Detailed Description