Two-dimensional organic heterogeneous crystal as well as preparation method and application thereof
Through molecular doping and light-induced color discoloration technology, the phase separation and lattice matching problems of two-dimensional organic heterostructure materials during the preparation process are solved, and the preparation of high-quality multi-color integrated two-dimensional organic hetero crystals is realized, simplifying the process flow.
Patent Information
- Application Number
- CN202510222795.9
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2025-02-27
- Publication Date
- 2025-07-08
AI Technical Summary
Existing two-dimensional organic heterostructure materials are prone to phase separation during the preparation process. Different lattice matching degrees lead to problems of heterostructure inhomogeneity and stability. In addition, the integration of red, green and blue primary color emission requires complex processes and is difficult to prepare on a large scale.
Using molecular doping and light-induced color discoloration technology, two-dimensional organic heterogeneous crystals are prepared in one step through the solution method, and heterogeneous structures are formed on the substrate using host molecules and guest molecules, and lattice consistency is regulated by ultraviolet light irradiation to achieve multi-color integration.
Two-dimensional organic heterogeneous crystals with clear heterointerfaces and flat surfaces were prepared, which avoided lattice mismatch, achieved the integration of three primary color emissions of red, green and blue, and simplified the preparation process.
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Figure CN120273032A_ABST
Abstract
Description
Technical Field
[0001] The present invention relates to the technical field of organic optoelectronic materials, and particularly relates to a two-dimensional organic heterocrystal and a preparation method and application thereof. Background Art
[0002] In the field of optoelectronics, two-dimensional heterostructures, as an innovative material structure, exhibit excellent performance and broad application potential. Compared with traditional two-dimensional materials based on a single component, two-dimensional heterostructure materials achieve tunability, multifunctionality, and high integration in performance by combining different material components, thus attracting extensive attention and research in multiple optoelectronic application fields such as signal modulation, energy storage, and photodetection.
[0003] In recent years, the research on two-dimensional heterostructure materials has mainly focused on inorganic material systems such as transition metal dichalcogenides and black phosphorus. These inorganic two-dimensional heterostructure materials have enabled the fabrication of high-performance devices such as micron-scale tungsten disulfide and tungsten diselenide heterostructures through precise lateral epitaxial growth techniques, and these devices exhibit excellent application performance in fields such as lateral p-n diodes and complementary inverters with high voltage gain. However, the further development and wide application of inorganic two-dimensional heterostructure materials still face many challenges. Among them, the strict requirements for lattice matching between different components during the lateral epitaxial growth process and the limited variety of available elements severely limit the diversity of inorganic two-dimensional heterostructure materials.
[0004] To address the above problems, organic semiconductor materials have gradually become a new hotspot in the research of two-dimensional heterostructure materials due to their unique advantages. Organic semiconductor materials possess remarkable characteristics such as a large surface area, long-range periodic order, and tunable physical and chemical properties, which provide favorable conditions for the development of two-dimensional heterostructures with complex hierarchical structures. By leveraging these characteristics of organic semiconductor materials, the integration of multiple functions such as signal transmission and processing can be achieved, thereby promoting the further development of the optoelectronics field. In addition, the energy transfer process in organic heterostructure materials provides a new approach for the precise control of spatial excitons. By optimizing the composition and structure of organic heterostructure materials, the distribution and transmission of spatial excitons can be precisely controlled along two in-plane paths, and then two-dimensional heterostructures with red, green, and blue emissions can be constructed, which have broad application prospects in signal transmission and processing within the visible spectrum.
[0005] However, although two-dimensional organic heterostructure materials have shown great potential in performance and application, their preparation methods still face many challenges. Existing organic lateral heterostructures are mainly prepared based on the sequential epitaxial growth technology between highly lattice-matched molecules, but the lattice constants between different molecules may be different, which makes phase separation easy to occur during the preparation process. This not only affects the uniformity and stability of the heterostructure, but also limits the possibility of its large-scale preparation. In addition, the preparation of two-dimensional organic heterostructures integrating red, green and blue primary color emissions usually requires multi-step reactions and complex process steps, and finding molecular systems with excellent luminescence performance and lattice adaptation to achieve heterogeneous crystals with multi-component luminescence integration is also a technical problem that needs to be solved urgently. Summary of the invention
[0006] In order to solve the above technical problems, the present invention provides a two-dimensional organic heterogeneous crystal and a preparation method and application thereof. The method prepares high-quality heterogeneous structures based on the synergistic effect of molecular doping and photoinduced color change, and can obtain a series of two-dimensional organic heterogeneous crystals with multi-color integrated emission. At the same time, the two-dimensional organic heterogeneous crystal has a flat surface, a clear heterogeneous interface and consistency of the lattice between different components.
[0007] The present invention is achieved through the following technical solutions:
[0008] The first aspect of the present invention provides a method for preparing a two-dimensional organic heterogeneous crystal, comprising the following steps:
[0009] (1) dissolving the host molecule in a good organic solvent to obtain a saturated host molecule stock solution; dissolving the guest molecule in a good organic solvent to obtain a saturated guest molecule stock solution;
[0010] (2) mixing the saturated host molecule stock solution and the saturated guest molecule stock solution obtained in step (1) at a volume ratio of (300-350):1, then adding a poor organic solvent, and dripping the obtained mixed solution onto a substrate, and obtaining a red-blue two-dimensional organic heterogeneous crystal after the solvent is completely evaporated; or
[0011] The saturated host molecule stock solution and the saturated guest molecule stock solution obtained in step (1) are mixed in a volume ratio of (0.8-1):1, and then a poor organic solvent is added, and the obtained mixed solution is dripped onto the substrate. After the solvent partially evaporates, the remaining mixed solution is irradiated with ultraviolet light, and after the solvent completely evaporates, a red-green two-dimensional organic heterogeneous crystal is obtained; or
[0012] Mix the saturated host molecule stock solution and the saturated guest molecule stock solution obtained in step (1) at a volume ratio of (300 - 350):1, then add a poor organic solvent. Drop the resulting mixed solution onto a substrate. After partial evaporation of the solvent, irradiate the remaining mixed solution with ultraviolet light. After complete evaporation of the solvent, a red-green-blue two-dimensional organic heterocrystal is obtained.
[0013] Further, in step (1), the host molecule is 2,6-diphenylanthracene.
[0014] Further, in step (1), the guest molecule is pentacene.
[0015] Further, in step (1), the good organic solvent is dichloromethane.
[0016] Further, in step (2), the poor organic solvent is selected from one or more of acetonitrile and water, preferably ethanol.
[0017] Further, in step (2), the volume ratio of the poor organic solvent to the host molecule stock solution is 1:(1.5 - 3).
[0018] Further, in step (2), the wavelength of the ultraviolet light is 375 - 405 nm.
[0019] Further, in step (2), the substrate is a silica substrate or a silicon substrate.
[0020] In a specific embodiment, the host molecule and the guest molecule can also be dissolved in a good organic solvent to obtain a saturated host-guest molecule stock solution. Add a poor organic solvent to the host-guest molecule stock solution. Drop the resulting mixed solution onto a substrate. After partial evaporation of the solvent, irradiate the remaining mixed solution with ultraviolet light. After complete evaporation of the solvent, a red-green two-dimensional organic heterocrystal is obtained.
[0021] Further, the mass ratio of the host molecule to the guest molecule is (1 - 1.5):1.
[0022] In a specific embodiment, in step (2), the saturated host molecule stock solution, the saturated guest molecule stock solution and the poor organic solvent can be mixed together to obtain a mixed solution.
[0023] The second aspect of the present invention provides a two-dimensional organic heterocrystal prepared by the preparation method described in the first aspect.
[0024] The third aspect of the present invention provides an application of the two-dimensional organic heterocrystal described in the second aspect in an optical waveguide.
[0025] Advantages of the present invention:
[0026] 1. The present invention provides a preparation method of a two-dimensional organic heterocrystal based on molecular doping. By using molecular doping and photochromic technology, a series of two-dimensional organic heterocrystals with multi-color integration are simply and quickly prepared in one step by a solution method, maintaining the lattice unity between different modules within the heterostructure and avoiding the phase separation phenomenon caused by lattice mismatch between different components within the heterostructure.
[0027] 2. Based on the two-dimensional organic heterocrystal as a carrier, the present invention realizes an efficient and simple method to regulate the waveguide characteristics dependent on the excitation position, and realizes the integration of a trichromatic light source with the two-dimensional organic heterocrystal as a carrier. Description of the Drawings
[0028] Figure 1 Fluorescence microscope image of the red-blue two-dimensional organic heterocrystal prepared in Example 1.
[0029] Figure 2 Scanning electron microscope image of the red-blue two-dimensional organic heterocrystal prepared in Example 1.
[0030] Figure 3 TEM image and SAED image of the red-blue two-dimensional organic heterocrystal prepared in Example 1; among them, (a) is the TEM image, and (b) and (c) are the SAED images of the corresponding positions.
[0031] Figure 4 Fluorescence microscope image of the red-green two-dimensional organic heterocrystal prepared in Example 2.
[0032] Figure 5 Scanning electron microscope image of the red-green two-dimensional organic heterocrystal prepared in Example 2.
[0033] Figure 6 X-ray diffraction patterns of the red-green two-dimensional organic heterocrystal (red-green heterocrystal), 2,6-diphenylanthracene, and pentacene prepared in Example 2.
[0034] Figure 7 Fluorescence microscope image of the red-green-blue two-dimensional organic heterocrystal prepared in Example 3.
[0035] Figure 8 Scanning electron microscope image of the red-green-blue two-dimensional organic heterocrystal prepared in Example 3.
[0036] Figure 9 Fluorescence microscope image of the red two-dimensional organic crystal prepared in Comparative Example 1.
[0037] Figure 10Fluorescence microscope image of the green two-dimensional organic crystal prepared in Comparative Example 2.
[0038] Figure 11 Fluorescence microscope image of the center region of the red-blue two-dimensional organic heterocrystal prepared in Example 1 with the excitation spot focused thereon and input (Ex) / output (Out 1-4) spectral signal diagrams.
[0039] Figure 12 Fluorescence microscope image of the edge region of the red-blue two-dimensional organic heterocrystal prepared in Example 1 with the excitation spot focused thereon and input (Ex) / output (Out 1-4) spectral signal diagrams.
[0040] Figure 13 Fluorescence microscope image of the corner region of the red-blue two-dimensional organic heterocrystal prepared in Example 1 with the excitation spot focused thereon and input (Ex) / output (Out 1-4) spectral signal diagrams. Detailed implementation manners
[0041] Unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by those of ordinary skill in the technical field to which this invention belongs. The terms used in the description of this invention herein are for the purpose of describing specific embodiments only and are not intended to limit the invention. The term "and / or" used herein includes any and all combinations of one or more of the related listed items.
[0042] The present invention will be further described below with reference to the accompanying drawings and specific embodiments, so that those skilled in the art can better understand the present invention and implement it, but the listed embodiments are not intended to limit the present invention.
[0043] Unless otherwise specified, the experimental methods used in the following examples are all conventional methods, and the materials, reagents, etc. used, unless otherwise specified, can be obtained from commercial channels.
[0044] The substrate used in the examples and comparative examples is a silica substrate.
[0045] Example 1
[0046] A method for preparing a red-blue two-dimensional organic heterocrystal, comprising the following steps:
[0047] (1) Dissolve 1 mg of 2,6-diphenylanthracene in 3 mL of dichloromethane and sonicate for 10 min, then filter to obtain a saturated 2,6-diphenylanthracene stock solution; dissolve 1 mg of pentacene in 3 mL of dichloromethane and sonicate for 10 min, then filter to obtain a saturated pentacene stock solution;
[0048] (2) Take 10 μL of the saturated pentacene stock solution and 1 mL of ethanol, add them to 3 mL of the saturated 2,6-diphenylanthracene stock solution, shake well, and drop the resulting mixed solution onto the substrate. After the solvent has completely evaporated, a red-blue two-dimensional organic heterocrystal is obtained on the substrate.
[0049] The red-blue two-dimensional organic heterocrystal prepared in Example 1 was characterized by fluorescence microscopy, scanning electron microscopy, transmission electron microscopy (TEM), and selected area electron diffraction (SAED). The test results are as Figures 1 - 3 shown. Figure 1 Figure 7 is a fluorescence microscopy image of the red-blue two-dimensional organic heterocrystal prepared in Example 1. Figure 2 Figure 8 is a scanning electron microscopy image of the red-blue two-dimensional organic heterocrystal prepared in Example 1. Figure 3 Figure 9 is the TEM image and SAED pattern of the red-blue two-dimensional organic heterocrystal prepared in Example 1. The test results show that the red-blue two-dimensional organic heterocrystal has a clear heterointerface and a flat surface, while maintaining the lattice consistency between the red and blue modules.
[0050] Example 2
[0051] A method for preparing a red-green two-dimensional organic heterocrystal, comprising the following steps:
[0052] (1) Dissolve 1 mg of 2,6-diphenylanthracene and 1 mg of pentacene together in 3 mL of dichloromethane and sonicate for 10 min, then filter to obtain a saturated host-guest molecule stock solution.
[0053] (2) Take 1 mL of ethanol and add it to 3 mL of the saturated host-guest molecule stock solution, shake well, and drop the resulting mixed solution onto the substrate. After partial evaporation of the solvent, irradiate the remaining mixed solution with ultraviolet light having a wavelength of 375 nm. After the solvent has completely evaporated, a red-green two-dimensional organic heterocrystal is obtained on the substrate.
[0054] The red-green two-dimensional organic heterocrystal prepared in Example 2 was characterized by fluorescence microscopy, scanning electron microscopy, and X-ray diffraction. The test results are as Figures 4 - 6 shown. Figure 4 Figure 10 is a fluorescence microscopy image of the red-green two-dimensional organic heterocrystal prepared in Example 2. Figure 5 Figure 11 is a scanning electron microscopy image of the red-green two-dimensional organic heterocrystal prepared in Example 2. Figure 6 Figure 12 is the X-ray diffraction pattern of the red-green two-dimensional organic heterocrystal (red-green heterocrystal), 2,6-diphenylanthracene, and pentacene prepared in Example 2. The test results show that the red-green two-dimensional organic heterocrystal has a clear heterointerface and a flat surface, while maintaining the lattice consistency between the red and green modules.
[0055] Example 3
[0056] A method for preparing a red-green-blue two-dimensional organic heterogeneous crystal, comprising the following steps:
[0057] (1) Dissolve 1 mg of 2,6-diphenylanthracene in 3 mL of dichloromethane and sonicate for 10 min, then filter to obtain a saturated 2,6-diphenylanthracene stock solution; dissolve 1 mg of pentacene in 3 mL of dichloromethane and sonicate for 10 min, then filter to obtain a saturated pentacene stock solution;
[0058] (2) Take 10 μL of the saturated pentacene stock solution and 1 mL of ethanol and add them to 3 mL of the saturated 2,6-diphenylanthracene stock solution, shake well, drop the resulting mixed solution onto a substrate, wait for part of the solvent to evaporate, then irradiate the remaining mixed solution with ultraviolet light with a wavelength of 375 nm. After the solvent has completely evaporated, a red-green-blue two-dimensional organic heterogeneous crystal is obtained on the substrate.
[0059] The red-green-blue two-dimensional organic heterogeneous crystal prepared in Example 3 was characterized by a fluorescence microscope and a scanning electron microscope. The test results are as shown in Figure 7 and Figure 8 shown. Figure 7 is a fluorescence microscope image of the red-green-blue two-dimensional organic heterogeneous crystal prepared in Example 3, Figure 8 is a scanning electron microscope image of the red-green-blue two-dimensional organic heterogeneous crystal prepared in Example 3. The test results show that the red-green-blue two-dimensional organic heterogeneous crystal has a clear heterogeneous interface and a flat surface.
[0060] Comparative Example 1
[0061] A method for preparing a red two-dimensional organic crystal, comprising the following steps:
[0062] (1) Dissolve 1 mg of 2,6-diphenylanthracene in 3 mL of dichloromethane and sonicate for 10 min, then filter to obtain a saturated 2,6-diphenylanthracene stock solution; dissolve 1 mg of pentacene in 3 mL of dichloromethane and sonicate for 10 min, then filter to obtain a saturated pentacene stock solution;
[0063] (2) Take 50 μL of the saturated pentacene stock solution and 1 mL of ethanol and add them to 3 mL of the saturated 2,6-diphenylanthracene stock solution, shake well, drop the resulting mixed solution onto a substrate, and after the solvent has completely evaporated, a red two-dimensional organic crystal is obtained on the substrate.
[0064] The red two-dimensional organic crystal prepared in Comparative Example 1 was characterized by a fluorescence microscope. The test results are as shown in Figure 9 shown. Figure 9Fluorescence microscope image of the red two-dimensional organic crystal prepared in Comparative Example 1. The test results show that no heterointerfaces are formed in the two-dimensional organic crystal.
[0065] Comparative Example 2
[0066] A method for preparing a green two-dimensional organic crystal, comprising the following steps:
[0067] (1) Dissolve 1 mg of 2,6-diphenylanthracene and 1 mg of pentacene together in 3 mL of dichloromethane and sonicate for 10 min, then filter to obtain a saturated host-guest molecule stock solution;
[0068] (2) Take 1 mL of ethanol and add it to 3 mL of the saturated host-guest molecule stock solution, shake well, drop the resulting mixed solution onto a substrate, and immediately irradiate the mixed solution with ultraviolet light having a wavelength of 375 nm. After the solvent has completely evaporated, a green two-dimensional organic crystal is obtained on the substrate.
[0069] Characterize the green two-dimensional organic crystal prepared in Comparative Example 2 using a fluorescence microscope. The test results are as Figure 10 shown, Figure 10 Fluorescence microscope image of the green two-dimensional organic crystal prepared in Comparative Example 2. The test results show that no heterointerfaces are formed in the two-dimensional organic crystal.
[0070] Test Example
[0071] Select a continuous laser with a 375 nm laser spot (diameter 2 - 4 microns) and focus it on the central region, edge region, and corner region of the red-blue two-dimensional organic heterocrystal prepared in Example 1 respectively. Output spectral signals (Out 1 - 4) are collected at the four edges of the crystal. The test results are as Figures 11 - 13 shown. The results show that the waveguide loss is proportional to the propagation distance. As can be seen from Figure 11 , when excited in the central region, the edge output signal shows a certain degree of blue shift compared to the input signal. As can be seen from Figure 12 , when excited in the edge region, the edge output signal shows no change in three directions and a red shift in one direction. As can be seen from Figure 13 , when excited in the corner region, the edge output signal remains unchanged compared to the excitation signal.
[0072] The present invention avoids the phenomenon of lattice mismatch between different components through a molecular doping strategy, realizes the preparation of a two-dimensional organic heterostructure, further realizes in-situ color change of crystal luminescence and constructs a heterointerface through a photoinduced color change strategy, and on this basis, realizes the preparation of a two-dimensional organic heterostructure with integrated trichromatic emission by combining the molecular doping and photoinduced color change strategies.
[0073] Obviously, the above embodiments of the present invention are merely examples for clearly illustrating the present invention, rather than limitations on the implementation manners of the present invention. Those skilled in the art should understand that other different forms of changes or variations can be made on the basis of the above description. It is not necessary and impossible to enumerate all implementation manners here. Any modifications, equivalent replacements, improvements, etc. made within the spirit and principle of the present invention shall be included in the protection scope of the claims of the present invention.
Claims
1. A method for preparing a two-dimensional organic heterocrystal, characterized in that, It includes the following steps: (1) Dissolve the host molecule in a good organic solvent to obtain a saturated host molecule stock solution; dissolve the guest molecule in a good organic solvent to obtain a saturated guest molecule stock solution; (2) Mix the saturated host molecule stock solution and the saturated guest molecule stock solution obtained in step (1) at a volume ratio of (300 - 350):1, then add a poor organic solvent, and drop the obtained mixed solution onto a substrate. After the solvent completely evaporates, a red-blue two-dimensional organic heterocrystal is obtained; or Mix the saturated host molecule stock solution and the saturated guest molecule stock solution obtained in step (1) at a volume ratio of (0.8 - 1):1, then add a poor organic solvent, and drop the obtained mixed solution onto a substrate. After partial evaporation of the solvent, irradiate the remaining mixed solution with ultraviolet light. After the solvent completely evaporates, a red-green two-dimensional organic heterocrystal is obtained; or Mix the saturated host molecule stock solution and the saturated guest molecule stock solution obtained in step (1) at a volume ratio of (300 - 350):1, then add a poor organic solvent, and drop the obtained mixed solution onto a substrate. After partial evaporation of the solvent, irradiate the remaining mixed solution with ultraviolet light. After the solvent completely evaporates, a red-green-blue two-dimensional organic heterocrystal is obtained.
2. The preparation method according to claim 1, characterized in that, In step (1), the host molecule is 2,6-diphenylanthracene.
3. The preparation method according to claim 1, characterized in that, In step (1), the guest molecule is pentacene.
4. The preparation method according to claim 1, wherein In step (1), the good organic solvent is dichloromethane.
5. The preparation method according to claim 1, wherein, In step (2), the poor organic solvent is selected from one or more of ethanol, acetonitrile, and water.
6. The preparation method according to claim 1, characterized in that, In step (2), the volume ratio of the poor organic solvent to the host molecule stock solution is 1:(1.5 - 3).
7. The preparation method according to claim 1, characterized in that, In step (2), the wavelength of the ultraviolet light is 375 - 405 nm.
8. The preparation method according to claim 1, characterized in that, In step (2), the substrate is a silica substrate or a silicon substrate.
9. A two-dimensional organic heterocrystal prepared by the preparation method according to any one of claims 1 - 8.
10. An application of the two-dimensional organic heterocrystal according to claim 9 in an optical waveguide.