A bichiral lead-based perovskite with second harmonic generation effect and a preparation method thereof
Patent Information
- Application Number
- CN202611010075.7
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2026-07-08
- Publication Date
- 2026-10-13
AI Technical Summary
然而，现有手性钙钛矿多为单手性体系，仅采用单一手性配体或阳离子，存在手性与SHG效应耦合不足、二次谐波转换效率偏低、制备周期长、结晶可控性差等问题
本发明提供了一种双手性铅基钙钛矿及其制备方法。本发明制备方法具有反应装置简单、原料易得、反应条件温和、成本低廉、目标产物易分离的优点，适合工业化生产。此外，采用本发明制备方法制得的双手性铅基钙钛矿均展现出非线性光学性质，在近红外光下，其二次谐波产生强度最高约为KDP的1.25倍。本发明克服了传统无机非线性光学化合物制备难度高以及有机非线性光学化合物分子结构复杂、合成工艺繁琐、制备周期长等问题，有利于对非线性光学化合物进行构效关系及实际应用研究。
Smart Images
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Abstract
Description
Technical Field
[0001] This invention relates to the field of chemical synthesis technology, specifically to a biphasic lead-based perovskite with second harmonic effect and its preparation method. Background Technology
[0002] Nonlinear optical materials are key functional materials for laser technology, optical communication, optical information storage, and chiral photonic devices. Their second harmonic generation (SHG) effect depends on the non-centrosymmetric structure of the material. Traditional inorganic nonlinear optical compounds suffer from harsh preparation conditions, while organic nonlinear optical compounds are characterized by complex molecular structures, cumbersome synthesis processes, long preparation cycles, and insufficient stability, which hinders the study of structure-property relationships and practical applications of nonlinear optical compounds.
[0003] Organic-inorganic lead-based perovskites possess advantages such as tunable structure, controllable bandgap, and mild preparation conditions, making them a research hotspot for novel nonlinear optical materials. Introducing chiral organic components can construct intrinsically non-centrosymmetric structures, achieving strong second harmonic response and chiral optical activity, which has significant application value in polarization detection, chiral recognition, and other fields. However, most existing chiral perovskites are monochiral systems, employing only a single chiral ligand or cation, resulting in problems such as insufficient coupling between chirality and the SHG effect, low second harmonic conversion efficiency, long preparation cycles, and poor crystallization controllability.
[0004] Based on this, the present invention provides a bipolar lead-based perovskite with second harmonic effect and its preparation method, aiming to solve the above-mentioned problems in the prior art. Summary of the Invention
[0005] The purpose of this invention is to provide a bipolar lead-based perovskite with second harmonic effect and its preparation method.
[0006] To achieve the above objectives, the technical solution adopted by the present invention is as follows: The general structural formula of the bipolar lead-based perovskite with second harmonic effect described in this invention is: ; In the formula: (Note: The original text contains some formatting errors and inconsistencies. A more accurate translation would require the full The carbon atoms are chiral carbon atoms.
[0007] The specific steps of the preparation method of bipolar lead-based perovskite with second harmonic effect described in this invention are as follows: lead iodide, bipolar ligand and hydroiodic acid are added to the reaction vessel; the mixture is heated under high temperature and refluxed; it is allowed to stand and naturally cooled to room temperature to obtain pure crystals of bipolar perovskite. The general structural formula of the bisexual ligand is as follows: ; In the formula: (Note: The original text contains some formatting errors and inconsistencies. A more accurate translation would require the full The carbon atoms are chiral carbon atoms.
[0008] Preferably, the general reaction formula for the preparation method of bipolar lead-based perovskite with second harmonic effect according to the present invention is: ; In the formula: (Note: The original text contains some formatting errors and inconsistencies. A more accurate translation would require the full The carbon atoms are chiral carbon atoms.
[0009] Preferably, in the preparation method of the bipolar lead-based perovskite with second harmonic effect of the present invention, the molar ratio of lead iodide, bipolar ligand and hydroiodic acid is 1:1:63.
[0010] Preferably, in the preparation method of bipolar lead-based perovskite with second harmonic effect according to the present invention, the heating reflux temperature is 80℃-150℃.
[0011] In a further preferred embodiment, in the method for preparing bipolar lead-based perovskite with second harmonic effect according to the present invention, the temperature condition for heating and reflux is 120℃-150℃.
[0012] In a further preferred embodiment, in the method for preparing bipolar lead-based perovskite with second harmonic effect according to the present invention, the heating reflux temperature is 120°C.
[0013] Preferably, in the preparation method of bipolar lead-based perovskite with second harmonic effect according to the present invention, the heating reflux time is 60-240 min.
[0014] In a further preferred embodiment, in the method for preparing bipolar lead-based perovskite with second harmonic effect according to the present invention, the heating and reflux time is 60-120 min.
[0015] In a further preferred embodiment, in the method for preparing bipolar lead-based perovskite with second harmonic effect according to the present invention, the heating reflux time is 120 min.
[0016] The beneficial effects of this invention are: This invention provides a biphasic lead-based perovskite and its preparation method. The preparation method of this invention has the advantages of simple reaction apparatus, readily available raw materials, mild reaction conditions, low cost, and easy separation of the target product, making it suitable for industrial production. Furthermore, the biphasic lead-based perovskites prepared by this method all exhibit nonlinear optical properties; under near-infrared light, their second harmonic generation intensity is approximately 1.25 times that of KDP. This invention overcomes the difficulties in preparing traditional inorganic nonlinear optical compounds and the problems of complex molecular structures, cumbersome synthesis processes, and long preparation cycles of organic nonlinear optical compounds, which is beneficial for structure-activity relationship research and practical application studies of nonlinear optical compounds. Attached Figure Description
[0017] Figure 1 This is a single-crystal structure diagram of compound 1; Figure 2 The image shows the X-ray powder diffraction pattern of compound 1. Figure 3 This is a single-crystal structure diagram of compound 2; Figure 4 The image shows the X-ray powder diffraction pattern of compound 2. Figure 5 Intensity versus particle size comparison diagrams were generated for the second harmonics of compound 1 and KDP samples; Figure 6 Intensity versus particle size comparison diagrams were generated for the second harmonics of compound 2 and KDP samples. Detailed Implementation
[0018] The technical solution of the present invention will be described in detail below with reference to specific embodiments. These embodiments are for explanation and illustration only and do not constitute a limitation on the technical solution of the present invention.
[0019] Example 1
[0020] The reaction route for the synthesis of compound 1 is as follows: ; The specific preparation method is as follows: (1) Add 922 mg PbI2 (2 mmol), 298 mg bisexual ligand 1 (2 mmol) and 15 mL HI (126 mmol) to a 100 mL round-bottom flask and place the round-bottom flask in an oil bath; (2) Turn on the condenser, heat to 120°C, and reflux for 120 min; (3) Remove the round-bottom flask and pour the reaction solution into a 25 mL beaker; (4) When placed in a room temperature environment and allowed to cool naturally, yellow needle-like crystals can be obtained with a yield of 920 mg and a yield of 45%.
[0021] Example 2
[0022] The reaction route for the synthesis of compound 1 is as follows: ; The specific preparation method is as follows: (1) Add 922 mg PbI2 (2 mmol), 298 mg bisexual ligand 1 (2 mmol) and 15 mL HI (126 mmol) to a 100 mL round-bottom flask and place the round-bottom flask in an oil bath; (2) Turn on the condenser, heat to 80°C, and reflux for 240 min; (3) Remove the round-bottom flask and pour the reaction solution into a 25 mL beaker; (4) When placed in a room temperature environment and allowed to cool naturally, yellow needle-like crystals can be obtained with a yield of 320 mg and a yield of 16%.
[0023] Example 3
[0024] The reaction route for the synthesis of compound 2 is as follows: ; The specific preparation method is as follows: (1) Add 922 mg PbI2 (2 mmol), 298 mg bisexual ligand 2 (2 mmol) and 15 mL HI (126 mmol) to a 100 mL round-bottom flask and place the round-bottom flask in an oil bath; (2) Turn on the condenser, heat to 120°C, and reflux for 120 min; (3) Remove the round-bottom flask and pour the reaction solution into a 25 mL beaker; (4) When placed in a room temperature environment and allowed to cool naturally, yellow needle-like crystals can be obtained with a yield of 850 mg and a yield of 42%.
[0025] Example 4
[0026] The reaction route for the synthesis of compound 2 is as follows: ; The specific preparation method is as follows: (1) Add 922 mg PbI2 (2 mmol), 298 mg bisexual ligand 2 (2 mmol) and 15 mL HI (126 mmol) to a 100 mL round-bottom flask and place the round-bottom flask in an oil bath; (2) Turn on the condenser, heat to 150°C, and reflux for 60 min; (3) Remove the round-bottom flask and pour the reaction solution into a 25 mL beaker; (4) When placed in a room temperature environment and allowed to cool naturally, yellow needle-like crystals can be obtained with a yield of 800 mg and a yield of 40%.
[0027] The single-crystal structure diagram of compound 1 is shown below. Figure 1 As shown, the X-ray powder diffraction pattern is as follows: Figure 2 As shown; the single-crystal structure diagram of compound 2 is shown below. Figure 3 As shown, the X-ray powder diffraction pattern is as follows: Figure 4 As shown.
[0028] To further verify the reliability of the present invention, the inventors conducted a series of experiments, as follows: 1. Experimental Methods Dry compounds 1 and 2 were ground and passed through 70-mesh, 100-mesh, 140-mesh, 200-mesh, 325-mesh, and 500-mesh sieves. Sample powders with particle sizes of 70-100 mesh, 100-140 mesh, 140-200 mesh, 200-325 mesh, and less than 500 mesh were taken respectively and tested using a visible-infrared second-order nonlinear optical spectrometer with an incident light wavelength of 1064 nm. KDP samples with the same mesh size range were taken and tested under the same conditions, and the second harmonic generation intensity of compounds 1 and 2 was compared with that of the KDP samples.
[0029] 2. Results and Discussion The comparison of second harmonic generation intensity and particle size for Compound 1 and KDP samples is shown in the figure below. Figure 5 As shown in the figure. The results show that compound 1 exhibits obvious second harmonic generation. Within the same particle size range, the second harmonic generation intensity of compound 1 is approximately 1.25 times that of KDP.
[0030] The comparison of second harmonic generation intensity and particle size for Compound 2 and KDP samples is shown in the figure below. Figure 6 As shown in the figure, the results show that compound 2 also exhibits a significant second harmonic generation phenomenon. Within the same particle size range, the second harmonic generation intensity of compound 2 is approximately 1.00 times that of KDP.
[0031] The above results demonstrate that the bipedal lead-based perovskites prepared in this study all exhibit nonlinear optical properties, with their second harmonic generation intensity reaching approximately 1.25 times that of KDP in the near-infrared region. Furthermore, the preparation method described in this study offers advantages such as simple reaction apparatus, readily available raw materials, mild reaction conditions, low cost, and easy separation of the target product. This research overcomes the difficulties in preparing traditional inorganic nonlinear optical compounds and the problems of complex molecular structures, cumbersome synthesis processes, and long preparation cycles associated with organic nonlinear optical compounds, thus facilitating the study of structure-activity relationships and practical applications of nonlinear optical compounds.
[0032] Although the present invention has been described in detail above with general descriptions, specific embodiments, and experiments, modifications or improvements can be made to it, which will be obvious to those skilled in the art. Therefore, all such modifications or improvements made without departing from the spirit of the present invention fall within the scope of protection claimed by the present invention.
Claims
1. A bipolar lead-based perovskite exhibiting second harmonic effect, characterized in that, The general structural formula of the bidirectional lead-based perovskite is as follows: ； In the formula: (Note: The original text contains some formatting errors and inconsistencies. A more accurate translation would require the full The carbon atoms are chiral carbon atoms.
2. The method for preparing bipolar lead-based perovskite with second harmonic effect as described in claim 1, characterized in that, The specific steps of the preparation method are as follows: lead iodide, bipolar ligand and hydroiodic acid are added to the reaction vessel; the mixture is heated under high temperature and refluxed; it is allowed to stand and naturally cooled to room temperature to obtain pure crystals of bipolar perovskite; The general structural formula of the bisexual ligand is as follows: ； In the formula: (Note: The original text contains some formatting errors and inconsistencies. A more accurate translation would require the full The carbon atoms are chiral carbon atoms.
3. The method for preparing bipolar lead-based perovskite with second harmonic effect according to claim 2, characterized in that, The general reaction formula is: ； In the formula: (Note: The original text contains some formatting errors and inconsistencies. A more accurate translation would require the full The carbon atoms are chiral carbon atoms.
4. The method for preparing bipolar lead-based perovskite with second harmonic effect according to claim 2, characterized in that, The molar ratio of lead iodide, bidirectional ligand, and hydroiodic acid is 1:1:
63.
5. The method for preparing bipolar lead-based perovskite with second harmonic effect according to claim 2, characterized in that, The temperature conditions for the heating reflux are 80℃-150℃.
6. The method for preparing bipolar lead-based perovskite with second harmonic effect according to claim 5, characterized in that, The temperature conditions for the heating reflux are 120℃-150℃.
7. The method for preparing bipolar lead-based perovskite with second harmonic effect according to claim 6, characterized in that, The temperature condition for the heating reflux is 120°C.
8. The method for preparing bipolar lead-based perovskite with second harmonic effect according to claim 2, characterized in that, The heating and reflux time is 60-240 min.
9. The method for preparing bipolar lead-based perovskite with second harmonic effect according to claim 8, characterized in that, The heating and reflux time is 60-120 min.
10. The method for preparing bipolar lead-based perovskite with second harmonic effect according to claim 9, characterized in that, The heating reflux time is 120 min.