An organic multicolor super-heterogeneous structure constructed based on radial assembly mechanism, preparation method and application in anti-counterfeiting labels
Through the organic multicolor superheterostructure construction method based on the radial assembly mechanism, the problem of difficulty in constructing complex hierarchical heterostructures in the prior art is solved, and photon barcodes with high encoding capacity are realized, which is suitable for a variety of advanced applications.
Patent Information
- Application Number
- CN202211320433.6
- Authority / Receiving Office
- CN · China
- Patent Type
- Patents(China)
- Current Assignee / Owner
- Filing Date
- 2022-10-26
- Publication Date
- 2025-04-04
- Estimated Expiration
- 2042-10-26
AI Technical Summary
The prior art is difficult to effectively build a complex hierarchical heterostructure with rich spatial segments, which limits the encoding capacity and depth anti-counterfeiting applications of advanced barcode applications.
Based on the radial assembly mechanism, a single-module heterostructure is constructed using organic molecules such as tris(octahydroxyquinoline)aluminum (Alq3) and Nile Red, and a multi-module integrated superheterostructure is formed through directional assembly to achieve a photon barcode with high encoding capacity.
It realizes photonic barcodes with high encoding capacity, has excellent performance, is suitable for optical communication, information encryption and high-end anti-counterfeiting fields, and has significant amplification and encoding capabilities and actual anti-counterfeiting application potential.
Smart Images
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Abstract
Description
Technical Field
[0001] The invention relates to an organic multicolor super-heterogeneous structure constructed based on a radial assembly mechanism, a preparation method and application in an anti-counterfeiting label, and belongs to the technical field of optical anti-counterfeiting devices. Background Art
[0002] Micro-nano photonic barcodes have attracted much attention due to their great potential in multiplexed bioanalysis, commodity tracking, and information security. Among them, micro-nano multicolor luminescent heterostructures have shown great potential in the field of photonic barcode construction because they can be easily distinguished by visually recognizable patterns.
[0003] Compared with single photon barcodes, multiple organic heterostructures can be spatially assembled in a directional manner under external stimulation to construct super heterostructures composed of multiple organic heterostructures, which makes them have broad development prospects in information encryption, coding capacity and anti-counterfeiting. At present, there are few reports on one-dimensional micro-nano multi-color super heterostructures with simple preparation methods; due to the limitations of structural complexity in the crystal growth process and host-guest molecular self-assembly, it is a great challenge to construct complex hierarchical heterostructures with rich spatial segments in a single microstructure. This will lead to limited coding capacity for advanced barcode applications, thereby limiting their deep anti-counterfeiting applications as advanced security labels.
[0004] Organic molecules have high photoluminescence quantum yield, tunable optical properties and fast light response. Their excellent flexibility and processability provide great advantages for the preparation of functional photonic devices, thus providing an excellent system for the preparation of micro-nano multi-color barcodes. In addition, the combination of different luminescent molecules in organic structures can be easily assembled through intermolecular interactions, which brings great flexibility to the realization of single organic heterostructures. At the same time, the excellent compatibility of organic materials enables the preparation of heterogeneous micro-nanostructures, thereby integrating different light-emitting modules into micro-nano heterostructures. Each organic heterostructure has similar coordination chemistry and easily identifiable multi-color emission peaks, which can establish an excellent multi-color heterogeneous emission organic system. Therefore, multi-segment organic heterostructures will provide a comprehensive understanding of the function-oriented structure of organic super heterostructure materials and open up a new way to manufacture advanced photonic components that can be used for anti-counterfeiting labels.
[0005] At present, there are not many reports on photonic anti-counterfeiting barcode materials and devices based on organic multi-color super heterostructures. Therefore, the present invention is proposed. Summary of the invention
[0006] In view of the shortcomings of the prior art, the present invention provides an organic multicolor super heterostructure constructed based on a radial assembly mechanism, a preparation method and an application in anti-counterfeiting labels. The present invention prepares a single-module organic multicolor heterojunction structure material by a simple and low-cost method, and then constructs a multi-module integrated super heterojunction structure material by directional assembly. The single-module organic multicolor heterojunction structure material is precisely positioned, aligned and oriented, presenting domain-controlled emission colors and recognizable patterns, thereby allowing the definition of high-coding capacity photonic barcodes. The preparation method of the present invention is simple, low-cost, and the resulting device has excellent performance, which can be well applied in the fields of optical communication, information encryption or high-end anti-counterfeiting.
[0007] The technical solution of the present invention is as follows:
[0008] An organic multicolor super heterostructure constructed based on a radial assembly mechanism, wherein the organic multicolor super heterostructure is a single-module heterostructure or a multi-module integrated super heterostructure; the single-module heterostructure is based on tris(octahydroxyquinoline)aluminum (Alq 3 ) is the main body and Nile red (NR) is the guest molecule, which are formed through π-π interaction; the multi-module integrated super heterostructure is formed by radial self-assembly of several single-module heterostructures.
[0009] According to the present invention, the main body of the single module heterostructure is tris(octahydroxyquinoline)aluminum (Alq 3 ), which has a large lattice spacing characteristic. The guest molecule of the single module heterostructure is Nile Red (NR), which has a strong π-π interaction with the host. The guest molecule Nile Red (NR) of the single module heterostructure has the characteristic of a suitable molecular size, and its molecular size is smaller than the lattice spacing of the host.
[0010] Preferably according to the present invention, the multi-module integrated super heterostructure is self-assembled by ≥2 single-module heterostructures.
[0011] Preferably, according to the present invention, the microstructure of the single-module heterostructure is a hexagonal prism, the length of the hexagonal prism is 0.2-20 μm, and the diameter of the hexagonal prism is 1-3 μm.
[0012] According to a preferred embodiment of the present invention, the red chromosome area of Nile red in the single module heterostructure accounts for 1.5% of tri(octahydroxyquinoline)aluminum (Alq 3 ) The proportion of the main body volume is 2%-90%.
[0013] The method for preparing the organic multicolor super heterostructure based on the radial assembly mechanism, the method for preparing the single module heterostructure comprises the steps of: 3), Nile red (NR) is fully dissolved in a good solvent to obtain a mixed solution; the mixed solution is injected into anti-solvent water, reacted, and the obtained reaction solution is centrifuged, washed, separated, and dried to obtain a single module heterogeneous structure.
[0014] According to the preferred embodiment of the present invention, the tri(octahydroxyquinoline)aluminum (Alq 3 ) and Nile red (NR) in a molar ratio of 1000-2000:1-20; preferably, the tri(octahydroxyquinoline)aluminum (Alq 3 ) and Nile Red (NR) in a molar ratio of 180-220:1.
[0015] According to the preferred embodiment of the present invention, the good solvent is tetrahydrofuran (THF); tri(octahydroxyquinoline)aluminum (Alq 3 ) and the volume ratio of the good solvent is 1:(5-10)mmol / L.
[0016] Preferably according to the present invention, the volume ratio of the mixed liquid to water is 0.5-1.2:4-10.
[0017] According to the present invention, preferably, the reaction temperature is 0-90°C and the reaction time is 3-30min; preferably, the reaction time is 10-20min. Within this time range, the morphology of the product is relatively regular.
[0018] Preferably, according to the present invention, the microstructure of the single-module heterostructure is a hexagonal prism; the size of the hexagonal prism is controlled by changing the reaction temperature.
[0019] Preferably, the length of the hexagonal prism decreases when the reaction temperature is increased, and the length of the hexagonal prism increases when the reaction temperature is decreased.
[0020] According to the preferred embodiment of the present invention, by changing tri(octahydroxyquinoline)aluminum (Alq 3 ) and Nile Red (NR), or the reaction temperature to obtain single-module heterostructures with different chromosome volumes.
[0021] The method for preparing the organic multi-color super-heterogeneous structure constructed based on the radial assembly mechanism, the method for preparing the multi-module integrated super-heterogeneous structure comprises the steps of:
[0022] The single-module heterogeneous structure is fully dispersed in a protic solvent, and then centrifuged, washed, separated, and dried to obtain a multi-module integrated super heterogeneous structure; the protic solvent is deionized water, methanol or ethanol.
[0023] According to the present invention, single-module heterostructures are radially assembled in protic solvents.
[0024] Preferably according to the present invention, the mass ratio of the single module heterostructure to the volume ratio of the protic solvent is 1-3 mg / mL.
[0025] According to the preferred embodiment of the present invention, the drying condition is 70-90° C. for 2-10 minutes.
[0026] The above-mentioned organic multicolor super-heterostructure constructed based on the radial assembly mechanism is used in anti-counterfeiting labels.
[0027] Preferably, according to the present invention, the organic multicolor super-heterostructure constructed based on the radial assembly mechanism is used as a highly integrated intelligent response micro-device for data encryption and decryption or information security and anti-counterfeiting.
[0028] The technical features and beneficial effects of the present invention are as follows:
[0029] 1. The single-module heterostructure preparation method of the present invention is simple and has low cost. The present invention can adjust the size of the single-module heterostructure crystal by controlling the temperature of the reactants (while ensuring that other preparation conditions are within the scope of the present invention), and obtain a single-module heterostructure crystal with a relatively regular morphology; by controlling tri(octahydroxyquinoline)aluminum (Alq 3 The dyeing range is controlled by adjusting the molar ratio of tris(octahydroxyquinoline)aluminum (Alq 3 ) lattice, will not affect tri(octahydroxyquinoline)aluminum (Alq 3 ) crystal size. The single-module heterostructures prepared by the present invention are red and green crystals with different dyeing intervals. These super-heterostructures with domain-controlled emission colors and recognizable patterns can constitute spatially resolved photonic barcodes. Through a flexible epitaxial growth procedure (radial self-assembly), a super-heterostructure library is further obtained. By rationally modulating each building block with specific color and morphological characteristics, rich photonic barcodes with significantly amplified coding capabilities can be defined.
[0030] 2. The present invention uses easy-to-prepare, low-cost single-module heterostructure materials to prepare uniform multi-module integrated super-heterostructures based on sequential heteroepitaxial growth, without the need for complex surface functionalization or external fields. The present invention selects a suitable liquid dispersant, and under the premise of the stable existence of the single-module heterostructure, each single-module heterostructure forms directional hydrogen bonds with liquid molecules, and under the dual impetus of Brownian motion and hydrogen bonds, it can radially self-assemble to form a multi-module integrated super-heterostructure; finally, during the evaporation and drying process of the proton solvent, the directional face-to-face attraction between the single-module heterostructures formed by simple capillary or van der Waals attraction will lead to specific molecular recognition to form a clear arrangement, that is, a multi-module integrated super-heterostructure is obtained.
[0031] 3. The preparation method of the multi-module integrated super-heterostructure of the present invention is simple and low-cost; a variety of color barcodes are realized, which can be applied to anti-counterfeiting photonic barcode materials and devices with high coding capacity; the obtained device has excellent performance and can be well applied in the fields of optical communication, information encryption or high-end anti-counterfeiting. In order to construct a barcode that integrates rich structural and color information in a single super-heterostructure, a solution containing a single-module heterostructure with different structural and color characteristics is drop-cast on a substrate to induce directional self-assembly. The resulting one-dimensional multi-module integrated super-heterostructure presents an alternating inhomogeneous green / red pattern. According to the uncertainty and random characteristics of Brownian motion, blocks with different characteristics are randomly combined into one-dimensional separation chains, where the random sequence of blocks provides a good platform for constructing physical unclonable function tags. These super-heterostructures use different excitation wavelengths as encryption keys and defined patterns as output signals, demonstrating encoding / decoding functions at the microscopic scale. Considering the diversity and flexibility of the one-dimensional separation chains, these tiny barcodes will have a high coding capacity and are expected to be easy to identify and difficult to copy, showing great potential as "anti-counterfeiting labels" with practical anti-counterfeiting applications. BRIEF DESCRIPTION OF THE DRAWINGS
[0032] Figure 1 This is a SEM image of the single-module heterostructure grown at 0°C in Example 1.
[0033] Figure 2 This is a fluorescence microscopy image of the single-module heterostructure prepared in Example 2.
[0034] Figure 3 This is a SEM image of the single-module heterostructure grown at 30°C in Example 2.
[0035] Figure 4 This is a SEM image of the single-module heterostructure grown at 80°C in Example 3.
[0036] Figure 5 This is the SEM image of the multi-module integrated super-heterostructure in Example 4.
[0037] Figure 6 This is the SEM image of the multi-module integrated super-heterostructure in Comparative Example 1.
[0038] Figure 7 This is the SEM image of the trialuminum crystal prepared in Comparative Example 2. DETAILED DESCRIPTION
[0039] The present invention is further described below by means of specific examples, but is not limited thereto.
[0040] Unless otherwise specified, the raw materials used in the examples are conventional raw materials and can be obtained commercially; the methods used in the examples are all prior arts unless otherwise specified.
[0041] Example 1
[0042] A method for preparing an organic multicolor super heterostructure based on a radial assembly mechanism, the method for preparing a single module heterostructure comprising the steps of: dissolving tri(octahydroxyquinoline)aluminum in tetrahydrofuran at a concentration of 8mM; dissolving Nile red in tetrahydrofuran at a concentration of 1mM. The above solutions are mixed evenly at a molar ratio of tri(octahydroxyquinoline)aluminum and Nile red of 200:1 to obtain a mixed solution; injecting the mixed solution into anti-solvent water (the volume ratio of the mixed solution to the anti-solvent water is 1:5), and growing in an ice bath at 0°C for 20 minutes. After the reaction is completed, the obtained reaction solution is centrifuged, washed, separated, and vacuum dried to obtain a single module heterostructure.
[0043] The SEM image of the single module heterostructure prepared in this example is as follows: Figure 1 As shown in the figure, it can be seen that the single-module heterostructure obtained in this embodiment is in the shape of a hexagonal prism, with a length of about 20 microns and a diameter of about 3 microns.
[0044] In the single-module heterostructure prepared in this example, the red chromosome accounts for the main tri(octahydroxyquinoline)aluminum (Alq 3 ) volume ratio is about 10% (obtained by fluorescence microscopy).
[0045] Example 2
[0046] A method for preparing an organic multicolor super heterostructure based on a radial assembly mechanism, the method for preparing a single module heterostructure comprising the steps of: dissolving tri(octahydroxyquinoline)aluminum in tetrahydrofuran at a concentration of 8mM; dissolving Nile red in tetrahydrofuran at a concentration of 1mM. The above solutions are mixed evenly at a molar ratio of tri(octahydroxyquinoline)aluminum and Nile red of 200:1 to obtain a mixed solution; injecting the mixed solution into anti-solvent water (the volume ratio of the mixed solution to the anti-solvent water is 1:5), and growing at 30°C for 20 minutes. After the reaction is completed, the obtained reaction solution is centrifuged, washed, separated, and vacuum dried to obtain a single module heterostructure.
[0047] The fluorescence microscopy image of the single module heterostructure prepared in this example is as follows: Figure 2 As shown, it means that the red Nile Red is successfully doped into the green tris(octahydroxyquinoline)aluminum crystals.
[0048] In the single-module heterostructure prepared in this example, the red chromosome accounts for the main tri(octahydroxyquinoline)aluminum (Alq 3 ) volume ratio is about 60%.
[0049] The SEM image of the single module heterostructure prepared in this example is as follows: Figure 3As shown in the figure, it can be seen that the single-module heterostructure obtained in this embodiment is in the shape of a hexagonal prism, with a length of about 5 microns and a diameter of about 2.5 microns.
[0050] Example 3
[0051] A method for preparing an organic multicolor super heterostructure based on a radial assembly mechanism, the method for preparing a single module heterostructure comprising the steps of: dissolving tri(octahydroxyquinoline)aluminum in tetrahydrofuran at a concentration of 8mM; dissolving Nile red in tetrahydrofuran at a concentration of 1mM. The above solutions are mixed evenly at a molar ratio of tri(octahydroxyquinoline)aluminum and Nile red of 200:1 to obtain a mixed solution; injecting the mixed solution into anti-solvent water (the volume ratio of the mixed solution to the anti-solvent water is 1:5), and growing at 80°C for 20 minutes. After the reaction is completed, the obtained reaction solution is centrifuged, washed, separated, and vacuum dried to obtain a single module heterostructure.
[0052] The SEM image of the single module heterostructure prepared in this example is as follows: Figure 4 As shown in the figure, it can be seen that the single-module heterostructure obtained in this embodiment is in the shape of a hexagonal prism, the length of the hexagonal prism is 500 nanometers, and the diameter is about 1.2 microns.
[0053] In the single-module heterostructure prepared in this example, the red chromosome accounts for the main tri(octahydroxyquinoline)aluminum (Alq 3 ) volume ratio is about 90%.
[0054] Example 4
[0055] A method for preparing an organic multi-color super heterostructure based on a radial assembly mechanism, the method for preparing a multi-module integrated super heterostructure comprising the steps of:
[0056] 10 mg of the single-module heterostructure prepared in Example 2 was fully dispersed in 5 mL of methanol, and then centrifuged, washed, separated, and dried at 80° C. for 5 minutes to obtain a multi-module integrated super heterostructure.
[0057] The SEM image of the multi-module integrated super heterostructure obtained in this embodiment is as follows Figure 5 As shown in the figure, it can be seen that multiple segments of three aluminum crystals are radially assembled, and there are no obvious gaps in the structure of the multiple segments of microrods observed through a high-power microscope.
[0058] Example 5
[0059] A method for preparing an organic multi-color super heterostructure based on a radial assembly mechanism, the method for preparing a multi-module integrated super heterostructure comprising the steps of:
[0060] 10 mg of the single-module heterostructure prepared in Example 1 was fully dispersed in 5 mL of ethanol, and then centrifuged, washed, separated, and dried at 80° C. for 5 minutes to obtain a multi-module integrated super heterostructure.
[0061] Example 6
[0062] A method for preparing an organic multi-color super heterostructure based on a radial assembly mechanism, the method for preparing a multi-module integrated super heterostructure comprising the steps of:
[0063] 10 mg of the single-module heterostructure prepared in Example 1 was fully dispersed in 5 mL of deionized water, and then centrifuged, washed, separated, and dried at 80° C. for 5 minutes to obtain a multi-module integrated super heterostructure.
[0064] Comparative Example 1
[0065] A method for preparing an organic multi-color super heterostructure based on a radial assembly mechanism, the method for preparing a multi-module integrated super heterostructure comprising the steps of:
[0066] 10 mg of the single-module heterostructure prepared in Example 1 was fully dispersed in 5 mL of n-hexane, and then centrifuged, washed, separated, and dried at 80° C. for 5 minutes. No multi-module integrated super heterostructure was obtained, and the crystals were randomly dispersed on the substrate. Figure 6 As shown, it can be seen that the type of protic solvent used in the present invention plays an important role.
[0067] Comparative Example 2
[0068] A method for preparing an organic multicolor super heterostructure based on a radial assembly mechanism, the method for preparing a single module heterostructure comprising the steps of: dissolving tri(octahydroxyquinoline)aluminum in tetrahydrofuran at a concentration of 8 mM; taking 1 ml of the solution, injecting the solution into 5 mL of anti-solvent water, and growing at 80° C. for 20 minutes. After the reaction is completed, the obtained reaction solution is centrifuged, washed, separated, and vacuum dried to obtain trialuminum crystals.
[0069] The SEM image of the three aluminum crystals prepared in this comparative example is as follows Figure 7 As shown, there is no obvious change in crystal size before and after doping with Nile red.
Claims
1. An organic multicolor super heterostructure constructed based on radial assembly mechanism, characterized in that: The organic multicolor super heterostructure is a single-module heterostructure or a multi-module integrated super heterostructure; the single-module heterostructure is composed of tri(octahydroxyquinoline)aluminum (Alq3) as the main body and Nile red (NR) as the guest molecule through π-π interaction; the multi-module integrated super heterostructure is composed of several single-module heterostructures through radial self-assembly; The preparation method of the single-module heterostructure comprises the steps of: fully dissolving tri(octahydroxyquinoline)aluminum (Alq3) and Nile red (NR) in a good solvent to obtain a mixed solution; injecting the mixed solution into anti-solvent water, reacting, and centrifuging, washing, separating, and drying the obtained reaction solution to obtain the single-module heterostructure.
2. The organic multicolor super heterostructure constructed based on the radial assembly mechanism according to claim 1, characterized in that: The multi-module integrated super heterostructure is self-assembled by 2 or more single-module heterostructures.
3. The organic multicolor super heterostructure constructed based on the radial assembly mechanism according to claim 1, characterized in that: Includes one or more of the following conditions: i. The microstructure of the single-module heterostructure is a hexagonal prism, the length of the hexagonal prism is 0.2-20 μm, and the diameter of the hexagonal prism is 1-3 μm; ii. In the single-module heterostructure, the ratio of the red chromosome volume of Nile Red to the main volume of tris(octahydroxyquinoline)aluminum (Alq3) is 2%-90%.
4. The organic multicolor super heterostructure constructed based on the radial assembly mechanism according to claim 1, characterized in that: The method for preparing a single module heterostructure includes one or more of the following conditions: i. The molar ratio of tris(octahydroxyquinoline)aluminum (Alq3) to Nile red (NR) is 1000-2000:1-20; ii. The good solvent is tetrahydrofuran (THF); the volume ratio of tri(octahydroxyquinoline)aluminum (Alq3) to the good solvent is 1:(5-10)mmol / L; iii. The volume ratio of the mixed liquid to water is 0.5-1.2:4-10; iv. The reaction temperature is 0-90°C and the reaction time is 3-30min.
5. The organic multi-color super-heterostructure constructed based on the radial assembly mechanism according to claim 4, characterized in that: Includes one or more of the following conditions: i. The molar ratio of tris(octahydroxyquinoline)aluminum (Alq3) to Nile red (NR) is 180-220:1; ii. The reaction time is 10-20 minutes.
6. The organic multicolor super heterostructure constructed based on the radial assembly mechanism according to claim 1, characterized in that: The microstructure of the single module heterostructure is a hexagonal prism; the size of the hexagonal prism can be controlled by changing the reaction temperature; As the reaction temperature increases, the length of the hexagonal prism decreases; as the reaction temperature decreases, the length of the hexagonal prism increases.
7. The organic multi-color super-heterostructure constructed based on the radial assembly mechanism according to claim 1, characterized in that: Single-module heterostructures with different chromosome volumes were obtained by changing the molar ratio of tris(octahydroxyquinoline)aluminum (Alq3) and Nile red (NR) or the reaction temperature.
8. The method for preparing an organic multi-color super heterostructure based on a radial assembly mechanism as claimed in claim 1, wherein the method for preparing a multi-module integrated super heterostructure comprises the steps of: The single-module heterogeneous structure is fully dispersed in a protic solvent, and then centrifuged, washed, separated, and dried to obtain a multi-module integrated super heterogeneous structure; the protic solvent is deionized water, methanol or ethanol.
9. The method for preparing an organic multicolor super heterostructure based on a radial assembly mechanism according to claim 8, characterized in that: Includes one or more of the following conditions: i. The mass ratio of the single module heterostructure to the volume ratio of the protic solvent is 1-3 mg / mL; ii. Drying conditions are 70-90℃ for 2-10 minutes.
10. Application of the organic multicolor super heterostructure constructed based on the radial assembly mechanism as claimed in any one of claims 1 to 7 in anti-counterfeiting labels.
11. The use according to claim 10, characterized in that: The organic multicolor super-heterostructure constructed based on the radial assembly mechanism is used as a highly integrated intelligent response micro-device for data encryption and decryption or information security and anti-counterfeiting.