Preparation method, product and application of fluorescent organic heterojunction based on solution self-assembly
Through solution self-assembly technology, fluorescent organic heterojunctions were prepared using lattice matching and epitaxial growth modes, which solved the nucleation and combination problems of organic heterostructures and realized the application of multifunctional optical filters.
Patent Information
- Application Number
- CN202310576917.5
- Authority / Receiving Office
- CN · China
- Patent Type
- Patents(China)
- Current Assignee / Owner
- Filing Date
- 2023-05-22
- Publication Date
- 2025-09-23
- Estimated Expiration
- 2043-05-22
AI Technical Summary
Existing technologies make it difficult to accurately synthesize organic heterostructures, especially in multi-level organic low-dimensional crystalline materials. It is difficult to achieve light modulation and light processing, and the nucleation process is uneven and the complex epitaxial relationship of the material combination is difficult to control.
Using the solution self-assembly method, donor molecules such as 1,3,6,8-tetraphenylpyrene are mixed with acceptor molecules in a specific solvent. Through lattice-matched vertical and horizontal epitaxial growth modes and a reasonable sequential self-assembly strategy, fluorescent organic heterojunctions are prepared.
Phase separation and uniform nucleation were achieved during the multi-component self-assembly process, and multi-color and multi-mode organic heterostructures were prepared, which are suitable for optical filter devices and support the research and development of organic photonics.
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Figure CN116656343B_ABST
Abstract
Description
Technical Field
[0001] The present invention belongs to the field of micro-nano organic material preparation and photonics application, and specifically relates to a preparation method, product and application of a fluorescent organic heterojunction based on solution self-assembly. Background Art
[0002] So far, simple organic low-dimensional crystalline materials can have laser properties and optical waveguide behavior, realizing light generation and light transmission functions, but it is difficult to achieve light modulation and light processing.
[0003] Therefore, the precise synthesis of multi-level organic low-dimensional crystalline materials plays a vital role in the scientific research and practical application of organic integrated photonics. To address this issue, organic heterostructures with excellent photoelectric response properties have attracted widespread attention, combining the advantages of organic semiconductors, such as high color fastness and feasibility of large-scale preparation, with their significant advantages such as low-cost solution processability, light weight, mechanical flexibility, and tunable molecular structure. In organic heterostructures, the inherent properties of individual components are not utilized, but the performance of the device is achieved through the rational design of each component and the precise synthesis of micro-nanostructures. Over the past few decades, the development of organic heterojunctions has been mainly divided into branch structures, core-shell structures, and block structures. As building blocks of optoelectronic devices, they have been used in various fields, such as light-emitting diodes, organic field-effect transistors (OFETs), and organic photovoltaic cells (OPVs).
[0004] However, the precise synthesis of organic heterostructured nanomaterials remains challenging due to the difficulty in controlling the homogeneous / inhomogeneous nucleation process and the complex epitaxial relationship of different material combinations. Summary of the Invention
[0005] The purpose of this section is to summarize some aspects of the embodiments of the present invention and briefly introduce some preferred embodiments. Some simplifications or omissions may be made in this section and the abstract and title of this application to avoid obscuring the purpose of this section, the abstract and the title of the invention, and such simplifications or omissions should not be used to limit the scope of the present invention.
[0006] In view of the above problems and / or the problems existing in the prior art, the present invention is proposed.
[0007] Therefore, the object of the present invention is to overcome the deficiencies in the prior art and provide a method for preparing a fluorescent organic heterojunction based on solution self-assembly.
[0008] To solve the above technical problems, the present invention provides the following technical solution: a method for preparing a fluorescent organic heterojunction based on solution self-assembly, comprising:
[0009] Taking 1,3,6,8-tetraphenylpyrene as the donor molecule, weigh the raw materials according to the molecular substance ratio of 1,3,6,8-tetraphenylpyrene:acceptor molecule of 1-4:0.5-1;
[0010] A good organic solvent is added to the weighed raw materials, dissolved and mixed evenly to obtain a stock solution of organic micro-nano heterostructures with a concentration of 1 to 10 mmol / L;
[0011] Adding the stock solution to a poor organic solvent and shaking uniformly to prepare a mixed solution, wherein the volume ratio of the good organic solvent to the poor organic solvent in the stock solution is 1:6 to 1:1;
[0012] The prepared mixed solution is dropped onto a substrate, the crystal environment growth temperature is adjusted, and after the organic solvent evaporates, a variety of fluorescent organic heterojunctions are obtained.
[0013] As a preferred embodiment of the preparation method of the present invention, the receptor molecules include 1,2,4,5-tetracyanobenzene, tetrafluoroterephthalonitrile and octafluoronaphthalene.
[0014] As a preferred embodiment of the preparation method of the present invention, the good organic solvent includes dichloroethane, dichloromethane, chloroform, tetrahydrofuran and acetonitrile.
[0015] As a preferred embodiment of the preparation method of the present invention, the poor organic solvent includes ethanol, methanol, water, n-hexane and cyclohexane.
[0016] As a preferred embodiment of the preparation method of the present invention, the crystal growth environment temperature is adjusted, wherein the temperature range is -30°C to 100°C.
[0017] As a preferred embodiment of the preparation method of the present invention, the temperature is 10°C.
[0018] As a preferred embodiment of the preparation method of the present invention, the ratio of 1,3,6,8-tetraphenylpyrene to acceptor molecule is 3:1.
[0019] Another object of the present invention is to overcome the deficiencies in the prior art and provide a fluorescent organic heterojunction prepared by a preparation method.
[0020] Another object of the present invention is to overcome the deficiencies in the prior art and provide an application of a fluorescent organic heterojunction as an optical filter device.
[0021] Beneficial effects of the present invention:
[0022] (1) The present invention realizes the preparation of a fluorescent organic heterojunction based on solution self-assembly, which is suitable for optical filters prepared by organic heterostructures. By selecting appropriate donors and acceptors, vertical and horizontal epitaxial growth modes based on lattice matching, and a reasonable sequential self-assembly strategy, the problems of phase separation and homogeneous nucleation in the multi-component self-assembly process are solved, providing a way to realize the design and synthesis of organic heterostructures.
[0023] (2) The method of the present invention has wide universality. It uses simple two-component donor-acceptor materials and realizes multi-color and multi-mode organic heterogeneous combination structures, such as core-shell and branch-shaped organic heterogeneous structures, by controlling the external growth environment and the molar ratio of the main receptor. It also provides support for the realization of optical filter devices, which is beneficial to the research and development of organic photonics. BRIEF DESCRIPTION OF THE DRAWINGS
[0024] In order to more clearly illustrate the technical solutions of the embodiments of the present invention, the following briefly introduces the drawings required for describing the embodiments. Obviously, the drawings described below are only some embodiments of the present invention. Those skilled in the art can also derive other drawings based on these drawings without inventive effort. Among them:
[0025] Figure 1 This is a fluorescence microscope image of the TBP-TCNB blue-red branch heterojunction in Example 1 of the present invention.
[0026] Figure 2 This is the micro-area PL spectrum at the junction of the blue trunk and the red branches of the TBP-TCNB blue-red branch heterojunction in Example 1 of the present invention.
[0027] Figure 3 This is a high-angle annular dark field scanning transmission electron image (HAADF-STEM) of the TBP-TCNB blue-red branch heterojunction in Example 1 of the present invention.
[0028] Figure 4 These are fluorescence microscope images of TBP crystals and ordinary optical microscope images of TCNB crystals.
[0029] Figure 5 This is a fluorescence microscope image of the TBP-TCNB blue-green core-shell heterojunction in Example 2.
[0030] Figure 6 This is a fluorescence microscope image of the TBP-TFP two-dimensional lamellar core-shell heterojunction in Example 3.
[0031] Figure 7 This is a picture of the TBP-TFP two-dimensional sheet core-shell heterojunction optical waveguide performance test in Example 3.
[0032] Figure 8This is a fluorescence microscope image of the TBP-OFN blue-green core-shell heterojunction in Example 4.
[0033] Figure 9 Fluorescence microscope image of the blue grid-shaped nanowires prepared in Comparative Example 1.
[0034] Figure 10 Fluorescence microscope image of the blue grid-shaped nanowires prepared in Comparative Example 2. DETAILED DESCRIPTION
[0035] In order to make the above-mentioned objects, features and advantages of the present invention more obvious and easy to understand, the specific implementation methods of the present invention are described in detail below in conjunction with the embodiments of the specification.
[0036] In the following description, many specific details are set forth to facilitate a full understanding of the present invention. However, the present invention may also be implemented in other ways different from those described herein. Those skilled in the art may make similar generalizations without violating the connotation of the present invention. Therefore, the present invention is not limited to the specific embodiments disclosed below.
[0037] Secondly, the term "one embodiment" or "embodiment" herein refers to a specific feature, structure, or characteristic that may be included in at least one implementation of the present invention. The phrase "in one embodiment" appearing in various places throughout this specification does not necessarily refer to the same embodiment, nor does it refer to a separate or selective embodiment that is mutually exclusive of other embodiments.
[0038] In the present invention, 1,3,6,8-tetraphenylpyrene (TBP), 1,2,4,5-tetracyanobenzene (TCNB), octafluoronaphthalene (OFN), and tetrafluoroterephthalonitrile (TFP) are all common commercially available materials.
[0039] Example 1
[0040] 0.2 mmol (101.33 mg) of donor TBP and 0.1 mmol (35.64 mg) of acceptor TCNB were dissolved in 10 mL of dichloroethane (DCE), where the molar ratio of TBP to TCNB was 2:1;
[0041] The prepared DCE solution containing TBP and TCNB components was added to 10 mL of ethanol, with a volume ratio of DCE to ethanol of 1:1;
[0042] The obtained mixed solution was directly dropped onto a silicon wafer substrate in air at room temperature. After the solvent was evaporated, a TBP-TCNB organic blue-red branch heterojunction was obtained.
[0043] See also Figure 1 , is a fluorescence microscope image of the blue-red branch heterojunction provided in Example 1, and a micro-area PL test was performed on the junction of the blue trunk and the red branch (see Figure 2 ), under the excitation wavelength of 365nm, two peaks appeared in the micro-area fluorescence spectrum, with the peak values located at 463nm and 653nm, corresponding to the wavelength ranges of blue light and red light, confirming the existence of blue light and red light at the junction, thereby supplementing the construction and generation of the blue-red branch heterojunction.
[0044] In order to better study the blue-red branch heterojunction generated by TBP and TCNB, selected area electron diffraction tests were performed using high-resolution transmission electron microscopy, and high-angle annular dark field scanning transmission electron images (HAADF-STEM) (see Figure 3 ) to obtain the basic elemental composition information of the crystal. The organic blue-red branch structure contains five elements: C, N, O, Si, and Cl, which are typical elements of both organic semiconductor materials. The C element exists in both the trunk and the branches because both TBP and TCNB contain C. N is a unique element of TCNB, and the distribution of N elements shows that N is present in the red branches because TCNB does not emit light in the visible wavelength range, while TBP emits blue light (see Figure 4 ), so the red branches better illustrate this: they are a mixture of TBP and TCNB, while the blue trunk grows from TBP. Cl is a characteristic element of ethylene dichloride, O is a characteristic element of ethanol, and Si is likely an impurity element on the special copper mesh or in the glass bottle when preparing the solution. As can be seen from the image, Si is basically absent from the trunk or branches.
[0045] Example 2
[0046] 0.3 mmol (151.98 mg) of donor TBP and 0.1 mmol (17.82 mg) of acceptor TCNB were dissolved in 10 mL of dichloroethane (DCE), where the molar ratio of TBP to TCNB was 3:1;
[0047] The prepared DCE solution containing TBP and TCNB components was added to 10 mL of ethanol, with a volume ratio of DCE to ethanol of 1:1;
[0048] The obtained mixed solution was directly dropped onto a silicon wafer substrate in air at an ambient temperature of 10°C. After the solvent was evaporated, an organic blue-green core-shell heterojunction was obtained.
[0049] See also Figure 5 , which is a fluorescence microscope image of the TBP-TCNB blue-green core-shell heterojunction provided in Example 2.
[0050] Example 3
[0051] 0.2 mmol (101.33 mg) of donor TBP and 0.1 mmol (20.01 mg) of acceptor TFP were dissolved in 10 mL of dichloroethane (DCE), where the molar ratio of TBP to TFP was 2:1;
[0052] The prepared DCE solution containing TBP and TFP components was added to 10 mL of ethanol, with a volume ratio of DCE to ethanol of 1:1;
[0053] The obtained mixed solution is directly dropped onto a silicon wafer substrate at room temperature in air. After the solvent is evaporated, an organic two-dimensional sheet-like core-shell heterojunction is obtained.
[0054] Figure 6 This is a fluorescence image of a two-dimensional core-shell heterojunction;
[0055] Figure 7 This is a test picture of the optical waveguide performance of the TBP-TFP two-dimensional sheet core-shell heterojunction. It can be seen that the waveguide characteristics of the four-segment periodic blue-yellow heterostructure show asymmetric waveguide attenuation. Among them, the spectrum of the first yellow part on the left edge of the crystal mainly covers the green to yellow band (520-750nm), while the right edge of the crystal (6' spectrum) has a cyan band emission (420-500nm). It can be attributed to the transfer of radiation energy from the cyan band to the yellow band, especially the 1-6 band. In addition, the normalized spectra of 1-6 and 1'-6' show obvious spectral modulation effects. When the excitation light beam alternately illuminates the monochromatic segment and the heterojunction, the spectral band shows periodic extension and compression. This result shows that this multi-segment waveguide heterostructure also has the ability to serve as an optical filter device.
[0056] Example 4
[0057] 0.2 mmol (101.33 mg) of donor TBP and 0.1 mmol (27.21 mg) of acceptor OFN were dissolved in 10 mL of dichloroethane (DCE), where the molar ratio of TBP to TCNB was 2:1;
[0058] The prepared DCE solution containing TBP and OFN components was added to 10 mL of ethanol, with a volume ratio of DCE to ethanol of 1:1;
[0059] The obtained mixed solution was directly dripped onto a silicon wafer substrate in air at an ambient temperature of 10°C. After evaporation of the solvent, an organic blue-green core-shell heterojunction was obtained. TBP-OFN is a blue-green core-shell heterojunction fluorescence image, see Figure 8 .
[0060] Comparative Example 1
[0061] 0.2 mmol (101.33 mg) of donor TBP and 0.1 mmol (35.64 mg) of acceptor TCNB were dissolved in 10 mL of dichloroethane (DCE), where the molar ratio of TBP to TCNB was 2:1;
[0062] The prepared DCE solution containing TBP and TCNB components was added to 10 mL of ethanol, with a volume ratio of DCE to ethanol of 1:1;
[0063] The obtained mixed solution was directly dropped onto a silicon wafer substrate in air at 5°C. After evaporation of the solvent, no TBP-TCNB organic blue-red branch heterojunction was obtained, but Figure 9 The blue mesh-like nanowires are shown.
[0064] Comparative Example 2
[0065] The donor 1,2-ph2py (the same 1,2-ph2py disclosed in the literature: Song Wan. Design and synthesis of electroluminescent materials based on pyrene and research on stretchable OLEDs [D]. Nanjing University of Posts and Telecommunications, 2020.) and the acceptor TCNB were dissolved in 10 mL of dichloroethane (DCE), where the molar ratio of 1,2ph2py to TCNB was 0.2 mmol:0.1 mmol;
[0066] The prepared DCE solution containing 1,2ph2py and TCNB components was added to 10 mL of ethanol, with a volume ratio of DCE to ethanol of 1:1;
[0067] The obtained mixed solution was directly dropped onto a silicon wafer substrate in air at room temperature, and after evaporation of the solvent, the following was obtained: Figure 10 The red crystal shown, the donor material 1,2ph2py reacts with TCNB and it is found that no heterojunction can be produced under the same conditions.
[0068] In order to overcome the shortcomings of the existing technology in the preparation of organic micro-nano heterostructures, such as lattice mismatch, complex process, and uncontrollable nature, which are not conducive to widespread application, the present invention provides a method for constructing primary organic core-shell and branch heterostructures by using solution self-assembly and based on lattice matching vertical and horizontal epitaxial growth modes and a reasonable sequential self-assembly strategy. This method has sufficient versatility to achieve the integration of multiple materials, is simple, fast, and controllable, and realizes applications with potential for optical filters based on the prepared organic heterojunction.
[0069] The present invention utilizes the principle of similar molecular stacking patterns and structural compatibility within the same donor molecule system, lattice-matched vertical and horizontal epitaxial growth patterns, and a rational sequential self-assembly strategy to achieve the construction of various organic heterojunctions. The organic micro-nano heterostructures provided by the present invention are formed by two or more molecules driven by intermolecular non-covalent interactions. Due to their excellent compatibility and designability with different components, a broad material library, controllable intermolecular forces, tunable fluorescence wavelength, and low-cost solution-based preparation, they provide an excellent approach for the preparation of organic micro-nano heterojunctions and a solid material foundation for organic photonic integrated devices such as optical filters.
[0070] The present invention proposes a simple method using solution self-assembly and based on lattice-matched vertical and horizontal epitaxial growth modes and a reasonable sequential self-assembly strategy to construct primary organic core-shell and branch heterostructures. The method is low-cost, simple to prepare, and has universal applicability. It uses simple two-component donor-acceptor materials and controls the external growth environment and the molar ratio of the main acceptor to achieve multi-color and multi-mode organic heterogeneous combination structures. Based on the prepared organic heterostructures, multifunctional integrated organic optoelectronic devices are built.
[0071] It should be noted that the above embodiments are only used to illustrate the technical solutions of the present invention and are not intended to limit the present invention. Although the present invention has been described in detail with reference to the preferred embodiments, those skilled in the art should understand that the technical solutions of the present invention may be modified or replaced by equivalents without departing from the spirit and scope of the technical solutions of the present invention, and all of these should be included in the scope of the present invention.
Claims
1. A method for preparing a fluorescent organic heterojunction based on solution self-assembly, characterized in that: include, 1,3,6,8-tetraphenylpyrene is used as a donor molecule, and raw materials are weighed according to the molecular substance ratio of 1,3,6,8-tetraphenylpyrene:acceptor molecule of (2-3):1, wherein the acceptor molecule is one of 1,2,4,5-tetracyanobenzene, tetrafluoroterephthalonitrile and octafluoronaphthalene; A good organic solvent is added to the weighed raw materials, dissolved and mixed uniformly to obtain a stock solution of organic micro-nano heterostructures with a concentration of 1 to 10 mmol / L, wherein the good organic solvent is one of dichloroethane, dichloromethane, chloroform, tetrahydrofuran and acetonitrile; adding the stock solution to a poor organic solvent and shaking the mixture to obtain a mixed solution, wherein the volume ratio of the good organic solvent to the poor organic solvent in the stock solution is 1:1, and the poor organic solvent is one of ethanol, methanol, water, n-hexane and cyclohexane; The prepared mixed solution was dropped onto a substrate, and the crystal environment growth temperature was adjusted to 10°C. After the organic solvent evaporated, a variety of fluorescent organic heterojunctions were obtained.
2. The preparation method according to claim 1, wherein: The ratio of 1,3,6,8-tetraphenylpyrene to acceptor molecule is 3:
1.
3. The fluorescent organic heterojunction prepared by the preparation method according to claim 1 or 2.
4. Use of the fluorescent organic heterojunction according to claim 3 as an optical filter device.