CN105002558A - Second-order nonlinear optical crystal K2SbF2Cl3 and its preparation method and application - Google Patents
Second-order nonlinear optical crystal K2SbF2Cl3 and its preparation method and application Download PDFInfo
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- 229910052700 potassium Inorganic materials 0.000 claims 1
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- 235000019796 monopotassium phosphate Nutrition 0.000 abstract description 9
- 229910000402 monopotassium phosphate Inorganic materials 0.000 abstract description 5
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Abstract
本发明公开了一种无机晶体化合物K2SbF2Cl3及其制备方法和作为二阶非线性光学晶体材料的应用。其晶体空间群为P212121，晶胞参数为 α＝β＝γ＝90°，Z＝4，光学带隙为4.01eV，其粉末倍频效应为磷酸二氢钾的4倍，粉末的红外透光范围达到14微米。本发明以KF和SbCl3为起始反应物，采用水热法制备得到无机晶体化合物K2SbF2Cl3。该无机晶体化合物有较强的可相位匹配的二阶非线性光学效应；在可见光区和中红外光区有很大的透光窗口；具有较大的带隙和热稳定性；合成方法操作简单、原料利用率高、实验条件温和、产品纯度高；该晶体材料能广泛应用于光学领域。
The invention discloses an inorganic crystal compound K 2 SbF 2 Cl 3 , a preparation method thereof and an application as a second-order nonlinear optical crystal material. Its crystal space group is P2 1 2 1 2 1 , and its unit cell parameters are α=β=γ=90°, Z=4, the optical band gap is 4.01eV, the frequency doubling effect of the powder is 4 times that of potassium dihydrogen phosphate, and the infrared transmission range of the powder reaches 14 microns. The invention uses KF and SbCl 3 as initial reactants, and prepares the inorganic crystal compound K 2 SbF 2 Cl 3 by a hydrothermal method. The inorganic crystal compound has a strong second-order nonlinear optical effect that can be phase-matched; it has a large light transmission window in the visible light region and the mid-infrared region; it has a large band gap and thermal stability; the synthesis method is simple to operate , high raw material utilization rate, mild experimental conditions, and high product purity; the crystal material can be widely used in the optical field.
Description
技术领域technical field
本发明涉及一种二阶非线性光学晶体K2SbF2Cl3及其制备方法和应用，属于无机化学领域，也属于材料科学领域和光学领域。The invention relates to a second-order nonlinear optical crystal K 2 SbF 2 Cl 3 and its preparation method and application, belonging to the field of inorganic chemistry, and also belongs to the field of material science and optics.
背景技术Background technique
非线性光学效应起源于激光与介质的相互作用。当激光在具有非零二阶极化率的介质中传播时，会产生倍频、和频、差频、光参量放大等非线性光学效应。利用晶体的二阶非线性光学效应，可以制成二次谐波发生器、频率转换器、光学参量振荡器等非线性光学器件，在激光技术、大气监测和国防军事等众多领域，都有着重要的应用价值。无机非线性光学材料在二阶非线性光学材料的实用化研究中居主导地位。依据透光波段和适用范围，无机二阶非线性光学晶体材料可分为紫外光区非线性光学材料、可见光区非线性光学材料和红外光区非线性光学材料。目前已投入实用的紫外及可见光区的无机非线性光学材料有β-偏硼酸钡(BBO)、硼酸锂(LBO)、磷酸二氢钾(KDP)、磷酸钛氧钾(KTP)等，基本可以满足大多数实用的要求。但对于红外非线性光学材料来讲，离实用还有差距。原因在于现有的红外二阶非线性光学晶体材料，如AgGaS2、AgGaSe2和ZnGeP2等晶体，虽然具有很大的二阶非线性光学系数，在红外光区也有很宽的透过范围，但合成条件苛刻，不容易生长光学质量高的大单晶，特别是损伤阈值较低，因而不能满足二阶非线性光学晶体材料的实用化要求。而实现红外激光的频率转换又在国民经济、国防军事等领域有着重要的价值，如实现连续可调的分子光谱，拓宽激光辐射波长的范围，开辟新的激光光源等。因而寻找高激光损伤阈值的红外无机非线性光学材料的研究已成为当前非线性光学材料研究领域的一个重要课题。Nonlinear optical effects originate from the interaction between laser and medium. When the laser propagates in a medium with non-zero second-order polarizability, nonlinear optical effects such as frequency doubling, sum frequency, difference frequency, and optical parametric amplification will occur. Using the second-order nonlinear optical effect of crystals, nonlinear optical devices such as second-harmonic generators, frequency converters, and optical parametric oscillators can be made, which are of great importance in many fields such as laser technology, atmospheric monitoring, and national defense. application value. Inorganic nonlinear optical materials play a dominant role in the practical research of second-order nonlinear optical materials. According to the light transmission band and scope of application, inorganic second-order nonlinear optical crystal materials can be divided into ultraviolet region nonlinear optical materials, visible light region nonlinear optical materials and infrared region nonlinear optical materials. At present, inorganic nonlinear optical materials in the ultraviolet and visible light regions that have been put into practical use include β-barium metaborate (BBO), lithium borate (LBO), potassium dihydrogen phosphate (KDP), potassium titanyl phosphate (KTP), etc., which can basically Meet most practical requirements. But for infrared nonlinear optical materials, there is still a gap from practicality. The reason is that the existing infrared second-order nonlinear optical crystal materials, such as AgGaS 2 , AgGaSe 2 and ZnGeP 2 crystals, have a large second-order nonlinear optical coefficient and have a wide transmission range in the infrared region. However, the synthesis conditions are harsh, and it is not easy to grow large single crystals with high optical quality, especially the damage threshold is low, so it cannot meet the practical requirements of second-order nonlinear optical crystal materials. The realization of infrared laser frequency conversion is of great value in the fields of national economy, national defense and military affairs, such as realizing continuously adjustable molecular spectrum, broadening the range of laser radiation wavelengths, and opening up new laser light sources. Therefore, the search for infrared inorganic nonlinear optical materials with high laser damage threshold has become an important topic in the field of nonlinear optical materials research.
发明内容Contents of the invention
本发明的首要目的在于克服现有技术的缺点与不足，提供一种透光波段较宽、二阶非线性光学系数较大、能够实现相位匹配、容易制备且稳定性较好的无机晶体化合物K2SbF2Cl3及其制备方法。The primary purpose of the present invention is to overcome the shortcomings and deficiencies of the prior art, and provide an inorganic crystal compound K with a wide light transmission band, a large second-order nonlinear optical coefficient, phase matching, easy preparation and good stability. 2 SbF 2 Cl 3 and its preparation method.
本发明的另一目的在于提供所述的无机晶体化合物作为二阶非线性光学晶体材料的应用。Another object of the present invention is to provide the application of the inorganic crystal compound as a second-order nonlinear optical crystal material.
本发明的目的通过以下技术方案实现：The object of the present invention is achieved through the following technical solutions:
一种无机晶体化合物，分子式为K2SbF2Cl3。An inorganic crystalline compound with the molecular formula K 2 SbF 2 Cl 3 .
其晶体空间群为P212121。Its crystal space group is P2 1 2 1 2 1 .
其晶胞参数为α＝β＝γ＝90°，Z＝4。Its unit cell parameters are α=β=γ=90°, Z=4.
无机晶体化合物的光学带隙为4.01eV。The optical band gap of the inorganic crystalline compound is 4.01 eV.
其粉末倍频效应为磷酸二氢钾的4倍，粉末的红外透光范围达到14微米。The frequency doubling effect of its powder is 4 times that of potassium dihydrogen phosphate, and the infrared light transmission range of the powder reaches 14 microns.
一种制备上述无机晶体化合物的方法，包括以下步骤：将摩尔比为2：1的KF和SbCl3加入水热反应釜内，再加入盐酸与蒸馏水的混合溶液，其中HCl和H2O的体积比为1-2：1，将密闭的水热反应釜放入马福炉内，缓慢加热至180℃，恒温反应1-2天后，缓慢降至室温；反应结束后，用乙醇冲洗，干燥后即得到无机晶体化合物K2SbF2Cl3。A method for preparing the above-mentioned inorganic crystal compound, comprising the following steps: adding KF and SbCl in a molar ratio of 2: 1 into a hydrothermal reaction kettle, and then adding a mixed solution of hydrochloric acid and distilled water, wherein the volume of HCl and H 2 O The ratio is 1-2:1, put the closed hydrothermal reaction kettle into the muffle furnace, slowly heat up to 180°C, and after 1-2 days of constant temperature reaction, slowly drop to room temperature; after the reaction, rinse with ethanol and dry to get Inorganic crystal compound K 2 SbF 2 Cl 3 .
所述的降温方式为自然降温或以2-6℃/h的速率降至室温。The cooling method is natural cooling or cooling down to room temperature at a rate of 2-6 °C/h.
所述的无机晶体化合物作为二阶非线性光学晶体材料的应用。The application of the inorganic crystal compound as a second-order nonlinear optical crystal material.
本发明制备K2SbF2Cl3的反应方程式如下所示：The reaction equation for preparing K 2 SbF 2 Cl 3 in the present invention is as follows:
2KF+SbCl3→K2SbF2Cl3 2KF+SbCl 3 →K 2 SbF 2 Cl 3
本发明具有以下优点和有益效果：The present invention has the following advantages and beneficial effects:
1.本发明制得的无机晶体化合物具有较大的倍频效应(SHG)，Kurt-Perryz粉末倍频测试结果表明其粉末倍频效应大约为磷酸二氢钾(KDP)的4倍；1. The inorganic crystalline compound that the present invention makes has bigger frequency doubling effect (SHG), and Kurt-Perryz powder frequency doubling test result shows that its powder frequency doubling effect is about 4 times of potassium dihydrogen phosphate (KDP);
2.本发明制得的无机晶体化合物在可见光区和中红外光区有很宽的透过范围，粉末的红外透光范围达到14微米；2. The inorganic crystal compound prepared by the present invention has a wide transmission range in the visible light region and the mid-infrared light region, and the infrared transmission range of the powder reaches 14 microns;
3.本发明制得的无机晶体化合物不含结晶水，对空气稳定，不潮解，且热稳定性较好，能够实现相位匹配；3. The inorganic crystal compound prepared by the present invention does not contain crystal water, is stable to air, does not deliquesce, has good thermal stability, and can realize phase matching;
4.本发明利用水热制备法，具有操作简单、原料利用率高、实验条件温和以及产品纯度高等优点。4. The present invention uses a hydrothermal preparation method, which has the advantages of simple operation, high utilization rate of raw materials, mild experimental conditions and high product purity.
附图说明Description of drawings
图1为本发明K2SbF2Cl3的阴离子基团[SbF2Cl3]2-结构图。Fig. 1 is the anionic group [SbF 2 Cl 3 ] 2- structure diagram of K 2 SbF 2 Cl 3 in the present invention.
图2为本发明K2SbF2Cl3中阴离子基团[SbF2Cl3]2-的排列图。Fig. 2 is an arrangement diagram of the anionic group [SbF 2 Cl 3 ] 2- in K 2 SbF 2 Cl 3 of the present invention.
图3为本发明K2SbF2Cl3固体粉末的UV-Vis光谱图。Fig. 3 is a UV-Vis spectrum diagram of K 2 SbF 2 Cl 3 solid powder of the present invention.
图4为本发明K2SbF2Cl3固体粉末的ATR-FTIR光谱图。Fig. 4 is an ATR-FTIR spectrogram of K 2 SbF 2 Cl 3 solid powder of the present invention.
图5为本发明K2SbF2Cl3的热失重谱图。Fig. 5 is the thermogravimetric spectrum of K 2 SbF 2 Cl 3 of the present invention.
图6为本发明K2SbF2Cl3的SHG大小与颗粒度关系曲线图。Fig. 6 is a graph showing the relationship between SHG size and particle size of K 2 SbF 2 Cl 3 in the present invention.
具体实施方式Detailed ways
下面结合具体实施例及附图对本发明的技术方案作进一步详细的描述，但本发明的实施方式不限于此。The technical solution of the present invention will be further described in detail below in conjunction with specific embodiments and accompanying drawings, but the embodiments of the present invention are not limited thereto.
实施例1Example 1
将20mmol KF和10mmol SbCl3加入23mL的水热反应釜内，再加入2mL盐酸与蒸馏水的混合溶液，其中HCl：H2O＝1：1，将密闭的水热反应釜放入马弗炉内，经3h加热至180℃，恒温反应1天，关闭马福炉，自然冷却至室温；反应结束后，用乙醇冲洗，干燥后即得到无色晶体K2SbF2Cl3。Add 20mmol KF and 10mmol SbCl 3 into a 23mL hydrothermal reaction kettle, then add 2mL of a mixed solution of hydrochloric acid and distilled water, where HCl:H 2 O = 1:1, put the closed hydrothermal reaction kettle into the muffle furnace , heated to 180°C for 3 hours, reacted at constant temperature for 1 day, closed the muffle furnace, and cooled naturally to room temperature; after the reaction, washed with ethanol and dried to obtain colorless crystal K 2 SbF 2 Cl 3 .
实施例2Example 2
将20mmol KF和10mmol SbCl3加入23mL的水热反应釜内，再加入3mL盐酸与蒸馏水的混合溶液，其中HCl：H2O＝2：1，将密闭的水热反应釜放入马弗炉内，经3h加热至180℃，恒温反应2天，以6℃/h的降温速率缓慢冷却至室温；反应结束后，用乙醇冲洗，干燥后即得到无色晶体K2SbF2Cl3。Add 20mmol KF and 10mmol SbCl 3 into a 23mL hydrothermal reaction kettle, then add 3mL of a mixed solution of hydrochloric acid and distilled water, where HCl:H 2 O = 2:1, put the closed hydrothermal reaction kettle into the muffle furnace , heated to 180°C for 3 hours, reacted at constant temperature for 2 days, and slowly cooled to room temperature at a cooling rate of 6°C/h; after the reaction, washed with ethanol and dried to obtain colorless crystal K 2 SbF 2 Cl 3 .
实施例3Example 3
将10mmol KF和5mmol SbCl3加入23mL的水热反应釜内，再加入2mL盐酸与蒸馏水的混合溶液，其中HCl：H2O＝1：1，将密闭的水热反应釜放入马弗炉内，经3h加热至180℃，恒温反应1天，以2℃/h的降温速率缓慢冷却至室温；反应结束后，用乙醇冲洗，干燥后即得到无色晶体K2SbF2Cl3。Add 10mmol KF and 5mmol SbCl3 into a 23mL hydrothermal reaction kettle, then add 2mL of a mixed solution of hydrochloric acid and distilled water, where HCl: H2O =1:1, put the closed hydrothermal reaction kettle into the muffle furnace , heated to 180°C for 3 hours, reacted at constant temperature for 1 day, and cooled slowly to room temperature at a cooling rate of 2°C/h; after the reaction, washed with ethanol and dried to obtain colorless crystal K 2 SbF 2 Cl 3 .
样品测试：test sample:
上述实施例所制备的无机晶体化合物的非线性光学性质测试通过Kurtz-Perry粉末倍频测试方法进行。具体操作步骤如下：预先将待测样品K2SbF2Cl3晶体进行研磨，筛选出粒径大小约为100-125μm的粉末样品，然后将其装入两面都为透明玻璃的样品池内，以同等颗粒度的KDP粉末作为标准样品。用激光照射样品池，通过滤镜过滤掉基频光并使倍频光透过，倍频信号经光电倍增管收集后显示于示波器上。通过比较待测样品与标准样品的倍频信号的强弱，得到待测样品的倍频效应强度大小，Kurtz-Perry粉末倍频测试结果表明其粉末倍频效应大约为磷酸二氢钾(KDP)的4倍。The nonlinear optical properties of the inorganic crystal compounds prepared in the above examples were tested by the Kurtz-Perry powder frequency doubling test method. The specific operation steps are as follows: Grind the K 2 SbF 2 Cl 3 crystal of the sample to be tested in advance, screen out the powder sample with a particle size of about 100-125 μm, and then put it into a sample cell with transparent glass on both sides, with equal Granularity of KDP powder as a standard sample. The sample cell is irradiated with laser light, the fundamental frequency light is filtered out through the filter and the frequency doubled light is transmitted through, and the frequency doubled signal is collected by the photomultiplier tube and displayed on the oscilloscope. By comparing the strength of the frequency doubling signal of the sample to be tested and the standard sample, the frequency doubling effect of the sample to be tested is obtained. The Kurtz-Perry powder frequency doubling test results show that the powder frequency doubling effect is about potassium dihydrogen phosphate (KDP) 4 times.
相位匹配测试是通过比较待测样品的粒径大小与倍频信号强度大小的关系来确定的。待测样品K2SbF2Cl3晶体经过研磨后，通过不同孔径的筛子筛选成不同粒径范围的颗粒(具体粒径大小范围为20-40μm，40-60μm，60-80μm，80-100μm，100-125μm，125-150μm，150-200μm，200-300μm，300-400μm，400-500μm以及大于500μm)。测试不同粒径范围待测样品倍频信号的强度大小，通过比较它们之间的关系来初步判断待测化合物能否实现相位匹配。The phase matching test is determined by comparing the relationship between the particle size of the sample to be tested and the intensity of the double frequency signal. After the K 2 SbF 2 Cl 3 crystal of the sample to be tested is ground, it is screened through sieves with different apertures into particles of different particle size ranges (the specific particle size ranges are 20-40 μm, 40-60 μm, 60-80 μm, 80-100 μm, 100-125 μm, 125-150 μm, 150-200 μm, 200-300 μm, 300-400 μm, 400-500 μm and greater than 500 μm). Test the intensities of frequency-doubling signals of the samples to be tested in different particle size ranges, and compare the relationship between them to preliminarily judge whether the compounds to be tested can achieve phase matching.
所得的无机晶体化合物经过X-射线单晶结构测定，其分子式为K2SbF2Cl3，空间群为P212121；晶胞参数为 α＝β＝γ＝90°，Z＝4。其阴离子基团[SbF2Cl3]2-的结构如图1所示。图2为该化合物阴离子基团[SbF2Cl3]2-的排列图。该无机晶体化合物固体粉末的UV-Vis光谱图如图3所示，其固体粉末的ATR-FTIR光谱图如图4所示，该无机晶体化合物具有较大的光学带隙，约为4.01eV；粉末的红外吸收边可达14微米，其热失重谱图如图5所示，该无机晶体化合物在180℃以后才开始失重，因此具有较好的热稳定性。其SHG大小与颗粒度关系曲线的测试结果如图6所示，表明该化合物是可以实现相位匹配的。The obtained inorganic crystal compound has been determined by X-ray single crystal structure, its molecular formula is K 2 SbF 2 Cl 3 , its space group is P2 1 2 1 2 1 ; the unit cell parameters are α=β=γ=90°, Z=4. The structure of its anion group [SbF 2 Cl 3 ] 2- is shown in Figure 1 . Figure 2 is the arrangement diagram of the anion group [SbF 2 Cl 3 ] 2- of the compound. The UV-Vis spectrum of the solid powder of the inorganic crystal compound is shown in Figure 3, and the ATR-FTIR spectrum of the solid powder is shown in Figure 4. The inorganic crystal compound has a large optical band gap, about 4.01eV; The infrared absorption edge of the powder can reach 14 microns, and its thermal weight loss spectrum is shown in Figure 5. The inorganic crystal compound begins to lose weight only after 180°C, so it has good thermal stability. The test results of the relationship curve between SHG size and particle size are shown in Figure 6, which shows that the compound can achieve phase matching.
本发明所制备的化合物K2SbF2Cl3晶体的空间群为P212121，属于正交晶系。在晶体结构的最小不对称单元中，有两个K原子、一个Sb原子、两个F原子和三个Cl原子。每介Sb原子与周围的两个F原子和三个Cl原子形成畸变的四方锥构型，其中的轴配位原子是F2。由于Sb3+具有孤对电子，所有的Sb-X键(X＝F、Cl)都位于Sb原子的一侧。其中，Sb-F键的键长分别为1.958(2)和Sb-Cl键的键长分别为2.5613(11)、2.6490(11)和 The space group of the compound K 2 SbF 2 Cl 3 crystal prepared in the present invention is P2 1 2 1 2 1 , which belongs to the orthorhombic crystal system. In the smallest asymmetric unit of the crystal structure, there are two K atoms, one Sb atom, two F atoms, and three Cl atoms. Each Sb atom forms a distorted tetragonal pyramid configuration with the surrounding two F atoms and three Cl atoms, and the axial coordination atom is F2. Since Sb 3+ has a lone pair of electrons, all Sb-X bonds (X=F, Cl) are located on one side of the Sb atom. Among them, the bond lengths of Sb-F bonds are 1.958(2) and The bond lengths of Sb-Cl bonds are 2.5613(11), 2.6490(11) and
化合物阴离子基团在三维空间中的排列非常不规则，而正是由于这种不规则的排列方式才使得化合物呈现非中心对称的结构，从而使化合物表现出一定的二阶非线性光学效应。但另一方面也可以看出，同一个晶胞的四个阴离子基团中，有两个基团的轴向键(Sb-F2)接近和a轴平行的方向，而另外两个基团的轴向键(Sb-F2)的方向则和a轴方向几乎反平行了。这种排列方式使得每一个单独阴离子基团形成的偶极矩不能有效的叠加，从而导致化合物无法表现出很强的倍频效应。The arrangement of the anionic groups of the compound in three-dimensional space is very irregular, and it is precisely because of this irregular arrangement that the compound presents a non-centrosymmetric structure, so that the compound exhibits a certain second-order nonlinear optical effect. But on the other hand, it can also be seen that among the four anionic groups in the same unit cell, the axial bonds (Sb-F2) of two groups are close to the direction parallel to the a axis, while the axial bonds of the other two groups are The direction of the axial bond (Sb-F2) is almost antiparallel to the direction of the a-axis. This arrangement prevents the dipole moments formed by each individual anion group from being superimposed effectively, thus causing the compound to fail to exhibit a strong frequency-doubling effect.
总之，它具有优良的综合性能，可作为二阶非线性光学晶体材料加以应用。In short, it has excellent comprehensive properties and can be applied as a second-order nonlinear optical crystal material.
上面结合附图对本发明的实施方式作了详细说明，但是本发明并不限于所述实施方式，可在本领域的普通技术人员所具备的知识范围内，还可以在不脱离本发明宗旨的前提下做出各种变化。The embodiments of the present invention have been described in detail above in conjunction with the accompanying drawings, but the present invention is not limited to the embodiments, and can be within the scope of the knowledge of those of ordinary skill in the art, and without departing from the gist of the present invention. Make various changes below.
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