Anthracene-doped inverse opal structure thin film with function of rapidly preparing fluorescent pattern as well as preparation method and application of anthracene-doped inverse opal structure thin film

Abstract

The invention belongs to the technical field of inverse opal photonic crystal materials, and discloses an anthracene-doped inverse opal structure thin film with a function of rapidly preparing a fluorescent pattern, and a preparation method and application of the anthracene-doped inverse opal structure thin film. The film is formed by compounding a polyacrylate copolymer and a silicon dioxide photonic crystal and etching in hydrofluoric acid. The polyacrylate copolymer is obtained by carrying out bulk polymerization on polyethylene glycol monophenyl acrylate doped with 10-(1-naphthyl) anthracene-9-boric acid and ethoxylated trimethylolpropane triacrylate under the action of a photoinitiator, namely 2-hydroxy-2-methyl-1-phenylacetone. The film has great application potential in the aspects of visual optical anti-counterfeiting and programmable fluorescent switch integration, and is expected to become a new generation of optical anti-counterfeiting label due to the characteristics of rapid patterning and high brightness.

Description

Technical Field

[0001] This invention belongs to the field of inverse opal photonic crystal material technology, specifically relating to an anthracene-doped inverse opal structure thin film with rapid fluorescent pattern preparation function, its preparation method and application. Background Technology

[0002] Structural colors originate from the precise manipulation of light by the micro / nanostructures of materials (such as interference and diffraction), exhibiting unique, vivid, and angle-dependent colors that cannot be reproduced by traditional printing. On the other hand, fluorescent structures utilize special materials or patterns to emit light of predetermined colors and intensities under specific illumination (such as ultraviolet light), requiring specialized excitation equipment. The combination of these two technologies has been applied to anti-counterfeiting, creating visible structural colors as the primary anti-counterfeiting feature and hidden fluorescent patterns as secondary anti-counterfeiting features, thus providing a powerful "visible + hidden" dual protection that is difficult to counterfeit.

[0003] In the research of luminescent anti-counterfeiting materials, photonic crystals (PCs) exhibit an unbleachable color due to the periodic arrangement of their refractive index or dielectric constant on the wavelength scale. The photonic bandgap (PBG) generated by the Bragg diffraction effect can precisely control the propagation of light at specific wavelengths by reducing the group velocity and redistributing the photon density of states (PDOS). Furthermore, the excitation light absorption and steady-state emission characteristics of fluorescent materials (such as organic dyes, quantum dots, and rare-earth metal complexes) are directly affected by the PBG in the ultraviolet-visible region, indicating that PCs have great potential in modulating the photoluminescence (PL) of fluorophores.

[0004] In recent years, research on stimulus-responsive fluorescent materials has attracted widespread attention in the field of advanced anti-counterfeiting. Among them, polycyclic aromatic hydrocarbons (PAHs), including derivatives of anthracene and coumarin, have garnered significant interest due to their ability to spontaneously dimerize upon prolonged exposure to ultraviolet light (Chem. Eng. J. 2025;504:158772). They not only possess inherent stealth but can also be designed for the dynamic verification of complex signals, such as multicolor fluorescence and photoresponsive color changes. For example, Wen et al. have developed a stealthy information storage method in which ultraviolet light (365 nm) triggers the conversion of monomers into dimers in a polymer network containing anthracene moieties, thereby inducing programmable modulation of fluorescence (Nat. Commun. 2024;15:10821). This precise control of material synthesis and pattern encoding still requires in-depth mechanistic research. The rate of photodimerization is influenced by a variety of interdependent factors, including photochemical parameters, inherent molecular properties, and environmental regulation. Using PC with periodic nanostructures to enhance the light field and introducing nanoconfinement technology can significantly improve reaction efficiency and selectivity (Adv. Mater. 2017;29(17):1605349). If photons stay in the material for a longer time, the interaction between the material and the light will be enhanced. However, the fluorescent patterns prepared by the above methods generally require a long preparation time, have high energy consumption, poor pattern resolution, and insufficient color brightness, which greatly limits the practical application of this material. Summary of the Invention

[0005] To address the problems existing in the fluorescent structural color anti-counterfeiting materials prepared by the prior art, the primary objective of this invention is to provide anthracene-doped inverse opal structure film with the function of rapidly preparing fluorescent patterns. A periodic structure is introduced into the polymer matrix using a method of reverse replication of a SiO2-PC template, thus preparing a periodically ordered inverse opal structure. 10-(1-naphthyl)-anthracene-9-boronic acid (NABA), a derivative of naphthalene with phenylboronic acid terminals, is used as a fluorescent dopant. The monomer polyethylene glycol phenyl ether acrylate (PEGPEA) and the crosslinking agent ethoxylated trimethylolpropane triacrylate (ETPTA) are used as photopolymerizable matrices to construct an NABA-doped poly(PEGPEA-co-ETPTA) film, referred to as a PEN film.

[0006] Another object of the present invention is to provide a method for preparing anthracene-doped inverse opal structure thin films with rapidly prepared fluorescent patterns as described above.

[0007] Another objective of this invention is to provide an anthracene-doped inverse opal structure film with rapidly prepared fluorescent patterns for use in visual optical anti-counterfeiting and programmable fluorescent switch integration. This film has great application potential, and its rapid patterning and high brightness characteristics are expected to make it a new generation of optical anti-counterfeiting labels.

[0008] The objective of this invention is achieved through the following technical solution:

[0009] An anthracene-doped inverse opal structure film with the function of rapidly preparing fluorescent patterns is obtained by compositing a polyacrylate copolymer with a silica (SiO2) photonic crystal and etching it in hydrofluoric acid. The polyacrylate copolymer is obtained by bulk polymerization of polyethylene glycol monophenyl acrylate (PEGPEA) monomer doped with 10-(1-naphthyl)anthracene-9-boronic acid (NABA) and crosslinking agent ethoxylated trimethylolpropane triacrylate (ETPTA) under the action of photoinitiator 2-hydroxy-2-methyl-1-phenylpropanone (1173, HMPP).

[0010] The silica photonic crystal is obtained by self-assembly of monodisperse SiO2 microspheres; the monodisperse SiO2 microspheres are obtained by two-step hydrolysis of tetraethyl orthosilicate (TEOS) under the catalysis of ammonia (NH3·H2O), including first forming a seed solution to complete the nucleation process, and then the seed particles continue to grow into spheres.

[0011] The above-mentioned method for preparing anthracene-doped inverse opal structure thin films with rapid fluorescent patterning capabilities includes the following steps: (1) Tetraethyl orthosilicate was added to a mixed solution consisting of anhydrous ethanol, deionized water and ammonia, and the reaction was carried out under heating and stirring conditions to prepare a seed solution; (2) Place the mixture A consisting of anhydrous ethanol, deionized water and ammonia in a container. Inject the seed solution obtained in step (1) into the mixture A under gentle magnetic stirring. Then inject tetraethyl orthosilicate and the mixture B consisting of anhydrous ethanol, deionized water and ammonia into the reaction system through a syringe pump. After complete injection, continue the reaction. After the reaction is completed, centrifuge to remove the supernatant. The collected microspheres are ultrasonically dispersed in ethanol and centrifuged again. Repeat the ultrasonic dispersion and centrifugation steps in ethanol three times. Finally, the microspheres are dried in an oven to obtain monodisperse SiO2 microspheres. (3) Prepare a dispersion of monodisperse SiO2 microspheres with ethanol, and use a dip-coating device to dip-coat the glass substrate surface at a constant rate of 2~4 μm / s in the dispersion to deposit SiO2 photonic crystals and obtain SiO2 photonic crystal templates. (4) Add 10-(1-naphthyl)anthracene-9-boronic acid (NABA) to a mixed solution formed by monomer polyethylene glycol monophenyl acrylate (PEGPEA), crosslinking agent ethoxylated trimethylolpropane triacrylate (ETPTA) and photoinitiator 2-hydroxy-2-methyl-1-phenylpropanone (1173, HMPP), shake and sonicate to obtain a prepolymer solution; (5) The prepolymer liquid obtained in step (4) is injected into the SiO2 photonic crystal template obtained in step (3), and then cured under ultraviolet light. After demolding, it is etched in 4% hydrofluoric acid to obtain an anthracene-doped inverse opal structure film.

[0012] The volume of tetraethyl orthosilicate in step (1) is 4-6 mL; the addition rate is 0.4-0.6 mL / min, and the stirring is carried out at a stirring speed of 600-650 rpm during the addition process; the volume ratio of anhydrous ethanol, deionized water and ammonia in the mixed solution is 50-70:1-10:1-2; the heating and stirring is carried out at 60-80℃ and the stirring speed is 300-350 rpm; the reaction time is 10-12 h; the particle size of SiO2 seeds in the seed solution is 40-60 nm.

[0013] In step (2), the volume ratio of anhydrous ethanol, deionized water, and ammonia in mixture A is 50-60:1:1; the volume of seed solution injected is 0.4-2.5 mL, and the seed solution is stirred at 400-500 rpm during injection; the injection speed of the syringe pump is 0.2-0.4 mL / min; the volume of tetraethyl orthosilicate injected is 20-30 mL; the volume ratio of tetraethyl orthosilicate to mixture B is 1:1-1.1; the volume ratio of anhydrous ethanol, deionized water, and ammonia in mixture B is 10:3:8; the reaction time is 5-6 h; the centrifugation is performed at a centrifugation rate of 8,000-10,000 rpm; and the oven drying is performed at 60-80℃ for 3 h.

[0014] In step (3), the mass fraction of the monodisperse SiO2 microspheres in the dispersion is 7.5-10%; the dip coating is carried out at a temperature of 55-65℃ and under windless conditions; the glass substrate is a 7.5×2.5 cm glass slide; the dip coating device is set with a dip coating height of 25-30 mm; and the dip coating is performed 1-3 times.

[0015] In step (4), the mass of 10-(1-naphthyl)anthracene-9-boric acid (NABA) is 0.5~10 mg; the volume ratio of the monomer polyethylene glycol monophenyl acrylate (PEGPEA), the crosslinking agent ethoxylated trimethylolpropane triacrylate (ETPTA), and the photoinitiator 2-hydroxy-2-methyl-1-phenylpropanone (1173, HMPP) is 1~2:2:0.03~0.04; the volume ratio of the monomer to the crosslinking agent is 1:1~2; the total volume of the monomer and the crosslinking agent is 100:1 to the volume ratio of the photoinitiator; the time for uniform oscillation is 1 min; and the time for ultrasonic homogenization is 1 min.

[0016] Step (5) involves injecting the prepolymer solution obtained in step (4) into the SiO2 photonic crystal template obtained in step (3). Specifically, the following steps are performed: the SiO2 photonic crystal template and another 7.5×2.5 cm glass slide are stacked perpendicularly together, separated and bonded together with interlayer adhesive, the thickness of which is 0.2~0.4 mm; the prepolymer solution is injected from the gap between the glass slide and the SiO2 photonic crystal template, and the prepolymer solution fills the interlayer between the glass slide and the photonic crystal template using capillary force; the settling time is 1~5 min; the UV lamp power is 12 W; the curing time is 20~60 s; the demolding body is prepared by the following steps: using a scalpel to cut and separate the edges of the glass slide and the film, and then using both hands to pry the glass slide apart; the etching time in 4% hydrofluoric acid is 3~4 h.

[0017] The above-mentioned anthracene-doped inverse opal structure thin film with rapid fluorescent pattern preparation function is applied in visual optical anti-counterfeiting and programmable fluorescent switch integration.

[0018] The present invention has the following advantages and effects compared with the prior art:

[0019] (1) Due to the stable hydrogen bond interaction between the polymer matrix and 10-(1-naphthyl)anthracene-9-boronic acid, the film obtained in this invention exhibits strong fluorescence stability under ultraviolet irradiation, wherein the fluorescence intensity decay of the film can be controlled to below 5% within 1 min of ultraviolet irradiation.

[0020] (2) The present invention proposes that a pure PEN film with a doping amount of 1 mg / mL of 10-(1-naphthyl)anthracene-9-boronic acid requires 30 min of continuous irradiation with 12W ultraviolet light to prepare a fluorescent pattern, while a PEN film with a doping amount of 0.5 mg / mL cannot be patterned, which proves the fluorescence stability of 10-(1-naphthyl)anthracene-9-boronic acid in the polymer structure.

[0021] (3) This invention utilizes anthracene-doped inverse opal structure thin films (PEN-IOPC) to systematically study the photodimerization kinetics of 10-(1-naphthyl)anthracene-9-boronic acid regulated by photonic crystals. The presence of a photonic bandgap increases the photon density, providing sufficient energy and time for the photoreaction of 10-(1-naphthyl)anthracene-9-boronic acid, thereby improving the photodimerization efficiency and enabling rapid photopatterning. In a classic example (Example 7), PEN-IOPC with a 530 nm reflection wavelength can produce a distinct fluorescence pattern after 5 minutes of UV exposure.

[0022] (4) A multidimensional optical encryption platform was developed on a single luminescent substrate by utilizing the synergistic interaction between photonic crystals and fluorescence responsiveness. This platform utilizes inverse opal with a customized photonic bandgap. For example, a "codebook communication" strategy inspired by Morse code encryption has been verified to protect the security of information communication under specific operating protocols. Furthermore, the combination of structural color and fluorescence intensity encoding, along with dynamic information modulation (e.g., solvent-responsive fluorescence switching), enables a high level of encryption for identity authentication through color-to-digit transposition. Attached Figure Description

[0024] Figure 1 The images show the infrared and fluorescence spectra of each substance, where (a) is the infrared spectrum of the monomers PEGPEA, ETPTA, and NABA described in Example 1, as well as the prepared PEN film, and (b) is the fluorescence spectrum of the PEN film during the first 16 seconds of the curing process.

[0025] Figure 2 The images show the spectra of PEN film and NABA, where (a) is the fluorescence spectrum of the PEN film described in Example 1 after continuous irradiation with ultraviolet light for two minutes, and (b) is the ultraviolet-visible absorption spectrum of NABA under ultraviolet lamp irradiation from 0 to 180 min.

[0026] Figure 3 The dynamic photodimerization process of the PEN film described in Example 2 was carried out by continuous irradiation under 365 nm ultraviolet light, which then led to fluorescence decay. The patterning effects of two PEN films (0.5 mg / mL and 1 mg / mL concentration) were compared.

[0027] Figure 4 The images show scanning electron microscope (SEM) images of the SiO2 microspheres synthesized in Example 3, high-resolution photographs of the SiO2 photonic crystal, and its reflection spectrum.

[0028] Figure 5 The image shows cross-sectional scanning electron microscope (SEM) images of anthracene-doped inverse opal (PEN-IOPC) prepared in Example 4 with different pull-out times.

[0029] Figure 6 The images show the reflection spectra of the photonic crystal prepared in Example 4 and the inverse opal structure prepared in Example 5.

[0030] Figure 7 The graphs show the performance of the thin film. (a) is a statistical graph of the fluorescence enhancement coefficient corresponding to different inverse opal pore sizes of the PEN thin film prepared in Example 6. (b) is a graph of the fluorescence intensity change of the PEN thin film prepared in Example 6 at different angles. (c) is a graph of the reflection spectrum change of the PEN thin film prepared in Example 6 at different angles. (d) is a statistical graph of the maximum reflection peak after 50 ethanol response cycle tests on the PEN-IOPC thin film.

[0031] Figure 8 The PEN-IOPC prepared in Example 7 x-y Real images of rapid preparation of fluorescent patterns under UV lithography at 5 min and 15 min.

[0032] Figure 9 The PEN-IOPC prepared in Example 8 is used for a "codebook communication" strategy diagram inspired by Morse code encryption, which can protect the security of information communication under a specific protocol.

[0033] Figure 10 This is a physical image of the stimulus-response color of the structural color and fluorescence intensity encoding matrix prepared in Example 9. Detailed Implementation

[0034] The present invention will be further described in detail below with reference to specific embodiments. It should be understood that the embodiments are only used to better explain the present invention and are not intended to limit the present invention.

[0035] This invention relates to an anthracene-doped inverse opal structure film capable of rapidly preparing fluorescent patterns. The anthracene-doped inverse opal structure film is prepared by copolymerizing 10-(1-naphthyl)anthracene-9-boric acid (NABA) with an acrylate monomer and a photonic crystal, followed by immersion in hydrofluoric acid and washing. The inverse opal structure is obtained by bulk polymerization of polyethylene glycol monophenyl acrylate (PEGPEA) and ethoxylated trimethylolpropane triacrylate (ETPTA) under the action of the photoinitiator 2-hydroxy-2-methyl-1-phenylprop-1-one (Darocur 1173, HMPP). The photonic crystal is obtained by self-assembly of SiO2 microspheres; the SiO2 microspheres are obtained by hydrolysis of tetraethyl orthosilicate in an alkaline solution. To effectively control the particle size, a modified Stöber method, a two-step seeding method, is used. This anthracene-doped inverse opal structure film has potential applications in the rapid preparation of fluorescent anti-counterfeiting patterns for multi-dimensional optical encryption anti-counterfeiting labels. Example 1

[0036] This embodiment discloses a method for preparing anthracene-doped polyacrylate (PEN) thin films, the specific steps of which are as follows:

[0037] First, 0.33 mL of polyethylene glycol monophenyl acrylate (PEGPEA), 0.67 mL of ethoxylated trimethylolpropane triacrylate (ETPTA), and 10 μL of 2-hydroxy-2-methyl-1-phenylpropanone (HMPP) were mixed in a 5 mL centrifuge tube to obtain a prepolymer solution for curing. 1 mg of 10-(1-naphthyl)anthracene-9-boric acid (NABA) was weighed and dissolved in a centrifuge tube containing 1 mL of the prepolymer solution, and the mixture was shaken for 1 min until homogeneous. The mixture was then shielded from light for 1 min and subjected to ultrasonic treatment to remove air bubbles for 1 min. Next, two 2.5 cm × 7.5 cm glass slides were stacked perpendicularly to each other, separated in the middle by a layer of 0.2 mm double-sided tape, and then bonded in place. Approximately 0.6 mL of the prepolymer solution was slowly added along one edge of each slide, allowing it to permeate the slide interlayer through capillary force, and the device was allowed to stand at room temperature for 1 min. The entire apparatus was then placed under a UV curing lamp, and the prepolymer was exposed to 12 W UV light for 20–60 s to obtain a PEN film. After curing, the PEN film was slowly peeled off the glass substrate using a scalpel.

[0038] Infrared absorption spectroscopy test, such as Figure 1 As shown in (a), 1631 cm is visible. -1 The disappearance of the infrared peak of the propylene double bond in the segment indicates the completion of PEN film polymerization. In this embodiment, the entire polymerization process of the prepolymer solution was carried out under ultraviolet light, and the changes in fluorescence intensity were recorded in situ using a detection instrument, such as... Figure 1 The fluorescence spectrum shown in (b) shows an initial increase followed by a decrease. This is because during the polymerization process, HMPP and NABA compete for ultraviolet energy absorption, leading to an increase in the fluorescence intensity of NABA. The subsequent decrease in fluorescence intensity is due to photodimerization of NABA. Figure 2 As shown in (a), the fluorescence change of the PEN film over a period of 140 s indicates that it has strong fluorescence stability. Figure 2 (b) shows the continuous change in absorbance of NABA in the characteristic absorption spectrum with increasing UV irradiation time, proving that photodimerization is occurring. Example 2

[0039] This embodiment discloses various methods for preparing anthracene-doped polyacrylate (PEN) films, the specific steps of which are as follows:

[0040] First, 2 mL of polyethylene glycol monophenyl acrylate (PEGPEA), 4 mL of ethoxylated trimethylolpropane triacrylate (ETPTA), and 600 μL of 2-hydroxy-2-methyl-1-phenylpropanone (HMPP) were mixed in a 10 mL centrifuge tube to obtain a prepolymer solution for curing. 0.5 mg, 1 mg, 2.5 mg, 5 mg, 7.5 mg, and 10 mg of NABA were weighed and dissolved in six 5 mL centrifuge tubes containing 1 mL of the prepolymer solution, respectively, and shaken for 1 min until homogeneous. The mixture was then shielded from light for 1 min and subjected to ultrasonic treatment to remove air bubbles for 1 min. Next, two 2.5 cm × 2.5 cm glass slides were stacked perpendicularly to each other, separated in the middle by a layer of 0.2 mm double-sided tape, and then bonded in place. Approximately 0.6 mL of the prepolymer solution was slowly added along one edge of the glass slide, allowing it to permeate the slide interlayer through capillary force, and the device was allowed to stand at room temperature for 1 min. The entire apparatus was then placed under a UV curing lamp, and the prepolymer solution was exposed to 12 W UV light for 20–60 s to prepare a PEN film. After curing, the PEN film was slowly peeled off the glass substrate using a scalpel.

[0041] The results showed that, except for prepolymer solutions with NABA contents of 0.5 mg, 1 mg, and 2.5 mg, which could solidify into PEN films within 60 seconds, the prepolymer solutions with NABA contents of 5 mg, 7.5 mg, and 10 mg could not be successfully solidified into PEN films. This may be attributed to the photoinitiator's inability to successfully absorb ultraviolet light and generate free radicals at high NABA concentrations. Figure 3 As shown, PEN films with concentrations of 0.5 mg / mL and 1 mg / mL were used to illuminate a QR code pattern under a photomask for 30 min. Only the 1 mg / mL PEN film successfully produced a pattern. The principle behind this patterning is that NABA undergoes dimerization under continuous irradiation with 365 nm ultraviolet light, resulting in a decrease in fluorescence intensity. Example 3

[0042] This embodiment discloses a method for preparing SiO2 photonic crystals, the specific steps of which are as follows:

[0043] Monodisperse SiO2 microspheres were synthesized using a modified Stöber method. First, 4.4 mL of TEOS was slowly added to a mixed solution of 160 mL ethanol, 33 mL deionized water, and 3.3 mL ammonia, and the mixture was stirred at 60 °C for 10 hours to synthesize a seed solution. Then, under gentle magnetic stirring, 240 mL of a mixed solution containing ethanol, deionized water, and ammonia (160 mL ethanol + 40 mL deionized water + 40 mL ammonia) was introduced into a 500 mL three-necked flask. Then, specific volumes of the seed solution (x = 1.75, 1.5, 1.25, and 1 mL) were added. Solution A (20 mL TEOS) and solution B (10 mL ethanol + 3 mL deionized water + 8 mL ammonia) were simultaneously injected into the reaction system at a rate of 0.2 mL / min for 100 min using a syringe pump. After complete addition, the reaction was allowed to proceed for 5 h. The resulting dispersion was centrifuged at 8000 rpm to remove the supernatant. The collected microspheres were ultrasonically redispersed in ethanol for 30 min, centrifuged again, and this purification cycle was repeated three times. Finally, the microspheres were dried in an oven for subsequent applications. Photonic crystals were fabricated using a dip-coating method. A 10% (m / v) ethanol dispersion of SiO2 microspheres was prepared. The photonic crystals were deposited onto a glass substrate under controlled conditions (55°C, windless environment) using an immersion lifting device. The substrate was pulled at a constant rate of 2 μm / s within a set height of 30 mm, and this process was repeated three times.

[0044] like Figure 4 As shown in the scanning electron microscope, the above steps, by controlling the volume x of the seed solution, yielded SiO2 microspheres with different particle sizes ranging from 200 to 260 nm. After dip-coating, blue, cyan, green, and yellow-green SiO2 photonic crystals were obtained on a glass slide, as shown in the high-resolution image in the figure. The reflection spectra of the four photonic crystals are the maximum reflection wavelengths at 464 nm, 483 nm, 529 nm, and 546 nm, respectively. Example 4

[0045] This embodiment discloses a method for preparing anthracene-doped inverse opal structure thin films, the specific steps of which are as follows:

[0046] Monodisperse SiO2 microspheres were synthesized using a modified Stöber method. First, 4.4 mL of TEOS was slowly added to a mixed solution of 160 mL ethanol, 33 mL deionized water, and 3.3 mL ammonia, and the mixture was stirred at 60 °C for 10 hours to synthesize a seed solution. Then, under gentle magnetic stirring, 240 mL of a mixed solution containing ethanol, deionized water, and ammonia (160 mL ethanol + 40 mL deionized water + 40 mL ammonia) was introduced into a 500 mL three-necked flask. Next, 1.25 mL of the seed solution was added. Solution A (20 mL TEOS) and solution B (10 mL ethanol + 3 mL deionized water + 8 mL ammonia) were simultaneously injected into the reaction system at a rate of 0.2 mL / min using a syringe pump for 100 min. After complete addition, the reaction was allowed to proceed for 5 h. The resulting dispersion was centrifuged at 8000 rpm to remove the supernatant. The collected microspheres were redispersed in ethanol by sonication for 30 min, centrifuged again, and this purification cycle was repeated three times. Finally, the microspheres were dried in an oven for subsequent applications. Photonic crystals were fabricated using a dip-coating method. A 10% (m / v) ethanol dispersion of SiO2 microspheres was prepared. PC was deposited onto a glass substrate under controlled conditions (55°C, windless environment) using an immersion lifting device. The substrate was pulled at a constant rate of 2 μm / s within a set height of 30 mm. To investigate the thickness effect, the dip-coating process was repeated for 1, 2, and 3 cycles, respectively, yielding SiO2 photonic crystals named PC. 1.25-1 PC 1.25-2 and PC 1.25-3 .

[0047] 0.33 mL of PEGPEA, 0.67 mL of ETPTA, and HMPP (photoinitiator, 1% v / v) were mixed in a 5 mL centrifuge tube to obtain the prepolymer solution to be cured. 1 mg of NABA was weighed and dissolved in a centrifuge tube containing 1 mL of the above prepolymer solution, and the mixture was shaken for 1 min until homogeneous. The mixture was then shielded from light for 1 min and subjected to ultrasonication to remove air bubbles for 1 min. The resulting PC... 1.25-1 PC 1.25-2 and PC 1.25-3The prepolymer was perpendicularly stacked onto 2.5 cm × 7.5 cm glass slides, separated and bonded together with a layer of 0.2 mm double-sided tape. Approximately 0.6 mL of prepolymer solution was slowly added along one edge of each slide, allowing it to penetrate the slide interlayer via capillary force, and the apparatus was left to stand at room temperature for 1 min. Subsequently, the entire apparatus was placed under a UV curing lamp, exposing the prepolymer solution to 12 W UV light for 60 s to obtain a PEN film. After curing, the PEN film was slowly peeled from the glass substrate using a scalpel. It was then etched in 4% (v / v) hydrofluoric acid to obtain anthracene-doped inverse opal structure film. The film was washed and dried for later use.

[0048] like Figure 5 The scanning electron microscope image shows the structures of 7-layer inverse opal prepared by one Czochralski technique, 17-layer inverse opal prepared by two Czochralski techniques, and 51-layer inverse opal prepared by three Czochralski techniques. Example 5

[0049] This embodiment discloses a method for preparing anthracene-doped inverse opal structure thin films, the specific steps of which are as follows:

[0050] Monodisperse SiO2 microspheres were synthesized using a modified Stöber method. First, 4.4 mL of TEOS was slowly added to a mixed solution of 160 mL ethanol, 33 mL deionized water, and 3.3 mL ammonia, and the mixture was stirred at 60 °C for 10 hours to synthesize a seed solution. Then, under gentle magnetic stirring, 240 mL of a mixed solution containing ethanol, deionized water, and ammonia (160 mL ethanol + 40 mL deionized water + 40 mL ammonia) was introduced into a 500 mL three-necked flask. Then, 1 mL of the seed solution was added. Solution A (20 mL TEOS) and solution B (10 mL ethanol + 3 mL deionized water + 8 mL ammonia) were simultaneously injected into the reaction system at a rate of 0.2 mL / min using a syringe pump for 100 min. After complete addition, the reaction was allowed to proceed for 5 h. The resulting dispersion was centrifuged at 8000 rpm to remove the supernatant. The collected microspheres were redispersed in ethanol by sonication for 30 min, centrifuged again, and this purification cycle was repeated three times. Finally, the microspheres were dried in an oven for subsequent applications. Photonic crystals were fabricated using a dip-coating method. A 10% (m / v) ethanol dispersion of SiO2 microspheres was prepared. PC was deposited onto a glass substrate under controlled conditions (55°C, windless environment) using an immersion lifting device. The substrate was pulled at a constant rate of 2 μm / s within a set height of 30 mm. To investigate the thickness effect, the dip-coating process was repeated for 1, 2, and 3 cycles, respectively, yielding SiO2 photonic crystals named PC. 1-1 PC 1-2 and PC 1-3 .

[0051] Mix 0.33 mL PEGPEA, 0.67 mL ETPTA, and HMPP (photoinitiator, 1% v / v) in a 5 mL centrifuge tube to obtain the prepolymer solution for curing. Weigh 1 mg of NABA and dissolve it in a centrifuge tube containing 1 mL of the above prepolymer, and shake for 1 min until homogeneous. Protect the mixture from light for 1 min and remove air bubbles by sonication for 1 min. Then, as described above: PC 1-1 PC 1-2 and PC 1-3 The prepolymer was perpendicularly stacked onto 2.5 cm × 7.5 cm glass slides, separated and bonded together with a layer of 0.2 mm double-sided tape. Approximately 0.6 mL of prepolymer solution was slowly added along one edge of each slide, allowing it to penetrate the slide interlayer via capillary force, and the apparatus was left to stand at room temperature for 1 min. Subsequently, the entire apparatus was placed under a UV curing lamp, exposing the prepolymer solution to 12 W UV light for 60 s to obtain a PEN film. After curing, the PEN film was slowly peeled from the glass substrate using a scalpel. It was then etched in 4% (v / v) hydrofluoric acid to obtain anthracene-doped inverse opal structure film. The film was washed and dried for later use.

[0052] like Figure 6 As shown, the relationship between the reflection wavelength and the reflection intensity between SiO2 photonic crystal and PEN-IOPC increases with the increase of the number of microsphere layers. Example 6

[0053] This embodiment discloses various methods for preparing anthracene-doped inverse opal structured thin films, the specific steps of which are as follows:

[0054] Monodisperse SiO2 microspheres were synthesized using a modified Stöber method. First, 4.4 mL of TEOS was slowly added to a mixed solution of 160 mL ethanol, 33 mL deionized water, and 3.3 mL ammonia, and the mixture was stirred at 60 °C for 10 hours to synthesize a seed solution. Then, under gentle magnetic stirring, 240 mL of a mixed solution containing ethanol, deionized water, and ammonia (160 mL ethanol + 40 mL deionized water + 40 mL ammonia) was introduced into a 500 mL three-necked flask. Then, 0.5, 0.75, 1, 1.25, 1.5, 1.75, or 2 mL of the seed solution was added. Solution A (20 mL TEOS) and solution B (10 mL ethanol + 3 mL deionized water + 8 mL ammonia) were simultaneously injected into the reaction system at a rate of 0.2 mL / min for 100 min using a syringe pump. After complete addition, the reaction was allowed to proceed for 5 h. The resulting dispersion was centrifuged at 8000 rpm to remove the supernatant. The collected microspheres were ultrasonically redispersed in ethanol for 30 min, centrifuged again, and this purification cycle was repeated three times. Finally, the microspheres were dried in an oven for subsequent applications. Photonic crystals were fabricated using a dip-coating method. A 10% (m / v) ethanol dispersion of SiO2 microspheres was prepared. PC was deposited on a glass substrate under controlled conditions (55°C, windless environment) using an immersion lifting device. The substrate was pulled at a constant rate of 2 μm / s within a set height of 30 mm for 3 cycles to obtain SiO2 photonic crystals, which were named: PC. 0.5-3 PC 0.75-3 PC 1-3 PC 1.25-3 PC 1.5-3 PC 1.75-3 or PC 2-3 .

[0055] 0.33 mL of PEGPEA, 0.67 mL of ETPTA, and HMPP (photoinitiator, 1% v / v) were mixed in a 5 mL centrifuge tube to obtain a prepolymer solution for curing. 1 mg of NABA was weighed and dissolved in a centrifuge tube containing 1 mL of the prepolymer solution, and the mixture was shaken for 1 min until homogeneous. The mixture was shielded from light for 1 min and then sonicated to remove air bubbles for 1 min. The various photonic crystals obtained were then stacked perpendicularly to 2.5 cm × 7.5 cm glass slides, separated and fixed with a layer of 0.2 mm double-sided tape. Approximately 0.6 mL of the prepolymer solution was slowly added along one edge of the glass slide, allowing it to penetrate the slide interlayer through capillary force, and the device was left to stand at room temperature for 1 min. The entire device was then placed under a UV curing lamp, exposing the prepolymer solution to 12 W of UV light for 60 s to obtain a PEN film. After curing, the PEN film was slowly peeled off the glass substrate using a scalpel. Subsequently, anthracene-doped inverse opal structure films were obtained by etching in 4% (v / v) hydrofluoric acid. The films were then washed, dried, and set aside for later use. Each sample was named PEN-IOPC. 0.5-3 PEN-IOPC 0.75-3 PEN-IOPC 1-3 PEN-IOPC 1.25-3 PEN-IOPC 1.5-3 PEN-IOPC 1.75-3 Or PEN-IOPC 2-3 All of the above materials underwent individual fluorescence spectroscopy measurements.

[0056] like Figure 7 The figure shows the fluorescence enhancement coefficient statistics of the above samples. Data analysis shows the enhancement relationship between reflectance spectrum and fluorescence emission, while the fluorescence intensity variation and reflectance spectrum variation at different angles demonstrate the interaction between the enhancement behavior and the angle. Cyclic testing proves its stability. Example 7

[0057] This embodiment discloses a variety of rapid patterning strategies for anthracene-doped inverse opal structure thin films, as detailed below:

[0058] Monodisperse SiO2 microspheres were synthesized using a modified Stöber method. First, 4.4 mL of TEOS was slowly added to a mixed solution of 160 mL ethanol, 33 mL deionized water, and 3.3 mL ammonia, and the mixture was stirred at 60 °C for 10 hours to synthesize a seed solution. Then, under gentle magnetic stirring, 240 mL of a mixed solution containing ethanol, deionized water, and ammonia (160 mL ethanol + 40 mL deionized water + 40 mL ammonia) was introduced into a 500 mL three-necked flask. Then, 0.5, 0.75, 1, 1.25, 1.5, 1.75, or 2 mL of the seed solution was added. Solution A (20 mL TEOS) and solution B (10 mL ethanol + 3 mL deionized water + 8 mL ammonia) were simultaneously injected into the reaction system at a rate of 0.2 mL / min for 100 min using a syringe pump. After complete addition, the reaction was allowed to proceed for 5 h. The resulting dispersion was centrifuged at 8000 rpm to remove the supernatant. The collected microspheres were ultrasonically redispersed in ethanol for 30 min, centrifuged again, and this purification cycle was repeated three times. Finally, the microspheres were dried in an oven for subsequent applications. Photonic crystals were fabricated using a dip-coating method. A 10% (m / v) ethanol dispersion of SiO2 microspheres was prepared. The photonic crystals were deposited onto a glass substrate under controlled conditions (55°C, windless environment) using an immersion lifting device. The substrate was pulled at a constant rate of 2 μm / s within a set height of 30 mm for three cycles, yielding SiO2 photonic crystals, which were named: PC. 0.5-3 PC 0.75-3 PC 1-3 PC 1.25-3 PC 1.5-3 PC 1.75-3 or PC 2-3 .

[0059] 0.33 mL of PEGPEA, 0.67 mL of ETPTA, and HMPP (photoinitiator, 1% v / v) were mixed in a 5 mL centrifuge tube to obtain a prepolymer solution for curing. 1 mg of NABA was weighed and dissolved in a centrifuge tube containing 1 mL of the prepolymer solution, and the mixture was shaken for 1 min until homogeneous. The mixture was shielded from light for 1 min and then sonicated to remove air bubbles for 1 min. The various photonic crystals obtained were then stacked perpendicularly to 2.5 cm × 7.5 cm glass slides, separated and fixed with a layer of 0.2 mm double-sided tape. Approximately 0.6 mL of the prepolymer solution was slowly added along one edge of the glass slide, allowing it to penetrate the slide interlayer through capillary force, and the device was left to stand at room temperature for 1 min. The entire device was then placed under a UV curing lamp, exposing the prepolymer solution to 12 W of UV light for 60 s to obtain a PEN film. After curing, the PEN film was slowly peeled off the glass substrate using a scalpel. Subsequently, anthracene-doped inverse opal structure films were obtained by etching in 4% (v / v) hydrofluoric acid. The films were then washed, dried, and set aside for later use. Each sample was named PEN-IOPC. 0.5-3 PEN-IOPC 0.75-3 PEN-IOPC 1-3 PEN-IOPC 1.25-3 PEN-IOPC 1.5-3 PEN-IOPC 1.75-3 Or PEN-IOPC 2-3 .

[0060] The aforementioned PEN-IOPC x-y The images were exposed to 12 W ultraviolet light under black photomasks decorated with images of sunflowers, snowflakes, swans, deer, bulls, and airplanes, respectively, for 5 minutes and 15 minutes. Figure 8 As shown, PEN-IOPC 1-3 It corresponds to a reflection wavelength of 530 nm and can form a clear pattern in 5 minutes. Example 8

[0061] This embodiment discloses a rapid patterning strategy for various anthracene-doped inverse opal structure thin films, and the specific steps are as follows:

[0062] Monodisperse SiO2 microspheres were synthesized using a modified Stöber method. First, 4.4 mL of TEOS was slowly added to a mixed solution of 160 mL ethanol, 33 mL deionized water, and 3.3 mL ammonia, and the mixture was stirred at 60 °C for 10 hours to synthesize a seed solution. Then, under gentle magnetic stirring, 240 mL of a mixed solution containing ethanol, deionized water, and ammonia (160 mL ethanol + 40 mL deionized water + 40 mL ammonia) was introduced into a 500 mL three-necked flask. Then, 0.5, 0.75, 1, 1.25, 1.5, 1.75, or 2 mL of the seed solution was added. Solution A (20 mL TEOS) and solution B (20 mL ethanol / deionized water / ammonia mixture (10 mL ethanol + 3 mL deionized water + 8 mL ammonia)) were simultaneously injected into the reaction system at a rate of 0.2 mL / min using a syringe pump for 100 min. After complete addition, the reaction was carried out for 5 h. The resulting dispersion was centrifuged at 8000 rpm to remove the supernatant. The collected microspheres were ultrasonically redispersed in ethanol for 30 min, centrifuged again, and this purification cycle was repeated three times. Finally, the microspheres were dried in an oven for subsequent applications. Photonic crystals were fabricated by dip-coating. A 10% (m / v) ethanol dispersion of SiO2 microspheres was prepared. PC was deposited on a glass substrate under controlled conditions (55 °C, windless environment) using an immersion lifting device. The substrate was pulled at a constant rate of 2 μm / s within a set height of 30 mm for 3 cycles to obtain SiO2 photonic crystals, which were named: PC. 0.5-3 PC 0.75-3 PC 1-3 PC 1.25-3 PC 1.5-3 PC 1.75-3 or PC 2-3 .

[0063] 0.33 mL of PEGPEA, 0.67 mL of ETPTA, and HMPP (photoinitiator, 1% v / v) were mixed in a 5 mL centrifuge tube to obtain a prepolymer solution for curing. 1 mg of NABA was weighed and dissolved in a centrifuge tube containing 1 mL of the prepolymer solution, and the mixture was shaken for 1 min until homogeneous. The mixture was shielded from light for 1 min and then sonicated to remove air bubbles for 1 min. The various photonic crystals obtained were then stacked perpendicularly to 2.5 cm × 7.5 cm glass slides, separated and fixed with a layer of 0.2 mm double-sided tape. Approximately 0.6 mL of the prepolymer solution was slowly added along one edge of the glass slide, allowing it to penetrate the slide interlayer through capillary force, and the device was left to stand at room temperature for 1 min. The entire device was then placed under a UV curing lamp, exposing the prepolymer solution to 12 W of UV light for 60 s to obtain a PEN film. After curing, the PEN film was slowly peeled off the glass substrate using a scalpel. Subsequently, anthracene-doped inverse opal structure films were obtained by etching in 4% (v / v) hydrofluoric acid. The films were then washed, dried, and set aside for later use. Each sample was named PEN-IOPC. 0.5-3 PEN-IOPC 0.75-3 PEN-IOPC 1-3 PEN-IOPC 1.25-3 PEN-IOPC 1.5-3 PEN-IOPC 1.75-3 Or PEN-IOPC 2-3 .

[0064] like Figure 8 As shown, the PEN-IOPCx-y were irradiated with 12 W ultraviolet light under black photomasks with Arabic letter patterns of “1” and “0”, respectively, for 15 min each. Figure 9 The obtained anthracene-doped inverse opal structure film was respectively bonded to a "decryption book" arranged in the order of "Huarong Road". "0" was defined as "·" signal and "1" was defined as "—" signal. Morse code was used to encode and encrypt "010", "110" and "011". Example 9

[0065] This embodiment discloses a rapid patterning strategy for various anthracene-doped inverse opal structure thin films, and the specific steps are as follows:

[0066] Monodisperse SiO2 microspheres were synthesized using a modified Stöber method. First, 4.4 mL of TEOS was slowly added to a mixed solution of 160 mL ethanol, 33 mL deionized water, and 3.3 mL ammonia, and the mixture was stirred at 60 °C for 10 hours to synthesize a seed solution. Then, under gentle magnetic stirring, 240 mL of a mixed solution containing ethanol, deionized water, and ammonia (160 mL ethanol + 40 mL deionized water + 40 mL ammonia) was introduced into a 500 mL three-necked flask. Then, 0.5, 0.75, 1, 1.25, 1.5, 1.75, or 2 mL of the seed solution was added. Solution A (20 mL TEOS) and solution B (20 mL ethanol / deionized water / ammonia mixture (10 mL ethanol + 3 mL deionized water + 8 mL ammonia)) were simultaneously injected into the reaction system at a rate of 0.2 mL / min using a syringe pump for 100 min. After complete addition, the reaction was carried out for 5 h. The resulting dispersion was centrifuged at 8000 rpm to remove the supernatant. The collected microspheres were ultrasonically redispersed in ethanol for 30 min, centrifuged again, and this purification cycle was repeated three times. Finally, the microspheres were dried in an oven for subsequent use. Photonic crystals were fabricated by dip-coating. A 10% (m / v) ethanol dispersion of SiO2 microspheres was prepared. The photonic crystals were deposited on a glass substrate under controlled conditions (55°C, windless environment) using an immersion lifting device. The substrate was pulled at a constant rate of 2 μm / s within a set height of 30 mm for 3 cycles to obtain SiO2 photonic crystals, which were named: PC. 0.5-3 PC 0.75-3 PC 1-3 PC 1.25-3 PC 1.5-3 PC 1.75-3 or PC 2-3 .

[0067] 0.33 mL of PEGPEA, 0.67 mL of ETPTA, and HMPP (photoinitiator, 1% v / v) were mixed in a 5 mL centrifuge tube to obtain a prepolymer solution for curing. 1 mg of NABA was weighed and dissolved in a centrifuge tube containing 1 mL of the prepolymer solution, and the mixture was shaken for 1 min until homogeneous. The mixture was shielded from light for 1 min and then sonicated to remove air bubbles for 1 min. The various photonic crystals obtained were then stacked perpendicularly to 2.5 cm × 7.5 cm glass slides, separated and fixed with a layer of 0.2 mm double-sided tape. Approximately 0.6 mL of the prepolymer solution was slowly added along one edge of the glass slide, allowing it to penetrate the slide interlayer through capillary force, and the device was left to stand at room temperature for 1 min. The entire device was then placed under a UV curing lamp, exposing the prepolymer solution to 12 W of UV light for 60 s to obtain a PEN film. After curing, the PEN film was slowly peeled off the glass substrate using a scalpel. Subsequently, anthracene-doped inverse opal structure films were obtained by etching in 4% (v / v) hydrofluoric acid. The films were then washed, dried, and set aside for later use. Each sample was named PEN-IOPC. 0.5-3 PEN-IOPC 0.75-3 PEN-IOPC 1-3 PEN-IOPC 1.25-3 PEN-IOPC 1.5-3 PEN-IOPC 1.75-3 Or PEN-IOPC 2-3 .

[0068] The aforementioned PEN-IOPC x-y Nine randomly selected color blocks, each made into a 5×5 mm cube, are arranged on a 3×3 matrix. This color matrix can display a variety of colors under varying angles, ethanol, deionized water, and ultraviolet light. By using these color signals to encrypt different Arabic numerals and setting the color change pattern as a necessary condition for sequential verification, a highly secure anti-counterfeiting authentication label can be obtained.

[0069] like Figure 10 As shown, the matrix above is used for structural color and fluorescence intensity encoding as well as dynamic information modulation (e.g., solvent-responsive fluorescence switching). Different color encoding definitions are implemented in different display modes, and a high level of encryption can be achieved by combining digital encryption.

[0070] The above embodiments are preferred embodiments of the present invention, but the embodiments of the present invention are not limited to the above embodiments. Any changes, modifications, substitutions, combinations, or simplifications made without departing from the spirit and principle of the present invention shall be considered equivalent substitutions and shall be included within the protection scope of the present invention.

Claims

1. An anthracene-doped inverse opal structure thin film with rapid fluorescent patterning capability, characterized in that: The film is formed by combining a polyacrylate copolymer with a silica photonic crystal and etching it in hydrofluoric acid; the polyacrylate copolymer is obtained by bulk polymerization of polyethylene glycol monophenyl acrylate monomer doped with 10-(1-naphthyl)anthracene-9-boronic acid and crosslinking agent ethoxylated trimethylolpropane triacrylate under the action of photoinitiator 2-hydroxy-2-methyl-1-phenylpropanone.

2. The anthracene-doped inverse opal structure thin film with rapid fluorescent patterning function according to claim 1, characterized in that: The silicon dioxide photonic crystal is obtained by self-assembly of monodisperse SiO2 microspheres; the monodisperse SiO2 microspheres are obtained by two-step hydrolysis of tetraethyl orthosilicate under ammonia catalysis, including first forming a seed solution to complete the nucleation process, and then the seed particles continue to grow into spheres.

3. The method for preparing anthracene-doped inverse opal structure thin films with rapid fluorescent patterning function according to claim 1 or 2, characterized in that... The following steps are included: (1) Tetraethyl orthosilicate was added to a mixed solution consisting of anhydrous ethanol, deionized water and ammonia, and the reaction was carried out under heating and stirring conditions to prepare a seed solution; (2) Place the mixture A consisting of anhydrous ethanol, deionized water and ammonia in a container. Inject the seed solution obtained in step (1) into the mixture A under gentle magnetic stirring. Then inject tetraethyl orthosilicate and the mixture B consisting of anhydrous ethanol, deionized water and ammonia into the reaction system through a syringe pump. After complete injection, continue the reaction. After the reaction is completed, centrifuge to remove the supernatant. The collected microspheres are ultrasonically dispersed in ethanol and centrifuged again. Repeat the ultrasonic dispersion and centrifugation steps in ethanol three times. Finally, the microspheres are dried in an oven to obtain monodisperse SiO2 microspheres. (3) Prepare a dispersion of monodisperse SiO2 microspheres with ethanol, and use a dip-coating device to dip-coat the glass substrate surface at a constant rate of 2~4 μm / s in the dispersion to deposit SiO2 photonic crystals and obtain SiO2 photonic crystal templates. (4) Add 10-(1-naphthyl)anthracene-9-boric acid to a mixed solution formed by monomer polyethylene glycol monophenyl acrylate, crosslinking agent ethoxylated trimethylolpropane triacrylate and photoinitiator 2-hydroxy-2-methyl-1-phenylpropanone, shake and sonicate to obtain a prepolymer solution. (5) The prepolymer liquid obtained in step (4) is injected into the SiO2 photonic crystal template obtained in step (3), and then cured under ultraviolet light. After demolding, it is etched in 4% hydrofluoric acid to obtain an anthracene-doped inverse opal structure film.

4. The method for preparing anthracene-doped inverse opal structure thin films with rapid fluorescent patterning function according to claim 3, characterized in that: The volume of tetraethyl orthosilicate in step (1) is 4-6 mL; the addition rate is 0.4-0.6 mL / min, and the stirring is carried out at a stirring speed of 600-650 rpm during the addition process; the volume ratio of anhydrous ethanol, deionized water and ammonia in the mixed solution is 50-70:1-10:1-2; the heating and stirring is carried out at 60-80℃ and the stirring speed is 300-350 rpm; the reaction time is 10-12 h; the particle size of SiO2 seeds in the seed solution is 40-60 nm.

5. The method for preparing anthracene-doped inverse opal structure thin films with rapid fluorescent patterning function according to claim 3, characterized in that: In step (2), the volume ratio of anhydrous ethanol, deionized water, and ammonia in mixture A is 50-60:1:1; the volume of seed solution injected is 0.4-2.5 mL, and the seed solution is stirred at 400-500 rpm during injection; the injection speed of the syringe pump is 0.2-0.4 mL / min; the volume of tetraethyl orthosilicate injected is 20-30 mL; the volume ratio of tetraethyl orthosilicate to mixture B is 1:1-1.1; the volume ratio of anhydrous ethanol, deionized water, and ammonia in mixture B is 10:3:8; the reaction time is 5-6 h; the centrifugation is performed at a centrifugation rate of 8,000-10,000 rpm; and the oven drying is performed at 60-80℃ for 3 h.

6. The method for preparing anthracene-doped inverse opal structure thin films with rapid fluorescent patterning function according to claim 3, characterized in that: In step (3), the mass fraction of the monodisperse SiO2 microspheres in the dispersion is 7.5-10%; the dip coating is carried out at a temperature of 55-65℃ and under windless conditions; the glass substrate is a 7.5×2.5 cm glass slide; the dip coating device is set with a dip coating height of 25-30 mm; and the dip coating is performed 1-3 times.

7. The method for preparing anthracene-doped inverse opal structure thin films with rapid fluorescent patterning function according to claim 3, characterized in that: In step (4), the mass of 10-(1-naphthyl)anthracene-9-boric acid is 0.5~10 mg; the volume ratio of the monomer polyethylene glycol monophenyl acrylate, the crosslinking agent ethoxylated trimethylolpropane triacrylate, and the photoinitiator 2-hydroxy-2-methyl-1-phenylpropanone is 1~2:2:0.03~0.04; the volume ratio of the monomer to the crosslinking agent is 1:1~2; the total volume of the monomer and the crosslinking agent is 100:1 to the volume ratio of the photoinitiator; the time for uniform oscillation is 1 min; and the time for ultrasonic homogenization is 1 min.

8. The method for preparing anthracene-doped inverse opal structure thin films with rapid fluorescent patterning function according to claim 3, characterized in that: Step (5) involves injecting the prepolymer solution obtained in step (4) into the SiO2 photonic crystal template obtained in step (3). Specifically, the following steps are performed: the SiO2 photonic crystal template and another 7.5×2.5 cm glass slide are stacked perpendicularly together, separated and bonded together with interlayer adhesive, the thickness of which is 0.2~0.4 mm; the prepolymer solution is injected into the gap between the glass slide and the SiO2 photonic crystal template, and the prepolymer solution fills the interlayer between the glass slide and the photonic crystal template using capillary force; the settling time is 1~5 min; the UV lamp power is 12 W; the curing time is 20~60 s; the demolding body is prepared by the following steps: using a scalpel to cut and separate the edges of the glass slide and the film, and then using both hands to pry the glass slide apart; the etching time in 4% hydrofluoric acid is 3~4 h.

9. The application of anthracene-doped inverse opal structure thin film with rapid fluorescent pattern preparation function as described in claim 1 or 2 in visual optical anti-counterfeiting and programmable fluorescent switch integration.

Images