Photosensitive material and preparation method and application thereof

Abstract

The invention discloses a photosensitive material and a preparation method and application thereof. The photosensitive material is composed of a monomer and an aggregation-induced emission dye. The preparation method of the material comprises the following steps: uniformly mixing a monomer and an aggregation-induced emission dye solvent; and removing the solvent in the solution to form the photosensitive material. Based on a laser direct writing mode of the material, a structure with the precision capable of reaching hundreds of nanometers is manufactured by utilizing laser beams to induce polymerization of the photosensitive material, and meanwhile, the polymerized structure also has a relatively good luminescence characteristic and can be applied to the fields of luminescent functional devices, biomedicine and the like. The method is simple and low in cost, and the material can be used in the fields of 3D printing, photoetching or optical storage and the like.

Description

Technical Field

[0001] This invention relates to the technical field of optical materials, and in particular to photosensitive materials using aggregation-induced emission dyes as photosensitizers, as well as preparation methods and laser direct writing methods based on such materials. Background Technology

[0002] Aggregation-induced emission (AIE) dyes are a novel class of luminescent materials. They typically exhibit weak or no fluorescence emission in dilute solutions, but in aggregates or solid states, the restricted intramolecular motion suppresses nonradiative transition channels, leading to significantly enhanced fluorescence emission. AIE dyes in the aggregated state possess high fluorescence quantum yield, excellent photostability, and high sensitivity, making them widely applicable in fields such as optical storage, optoelectronics, biomedicine, and chemical sensing.

[0003] Two-photon polymerization (TPP) can arbitrarily construct three-dimensional structures, providing a key manufacturing method for realizing advanced light-emitting functional devices with good geometry. Typically, when fabricating fluorescent microstructures using TPP, dyes, luminescent polymers, and metal nanoparticles are doped into the photoresist system to induce fluorescence (CN 120928646 A, CN 120588485 A, CN120536131 A, CN 114621395 A). However, the addition of these substances not only increases the complexity of the manufacturing process but also affects the precision of the structure. Furthermore, the solubility and dispersion of the dopants in the photoresist can affect the fluorescence uniformity of the microstructure. Another approach is to use chemical bonds to link luminescent groups to monomers or functional components in the photoresist (Macromolecules 52, 3668 (2019)). However, this process is complex, and the introduction of other groups may affect the polymerization, thus impacting processing precision. To fabricate high-performance light-emitting devices, there is an urgent need to develop a photoresist system with sufficiently sensitive two-photon absorption, free of dopants and solvents—that is, an intrinsically luminescent photoresist system—to construct fluorescent three-dimensional structures. Currently, many fluorescent materials (carbon dots, perovskite quantum dots, and carbon nitride, etc.) have been found to possess high photoinducibility, capable of inducing polymerization reactions under illumination, and also exhibiting luminescent properties (Mater. TodayPhys. 20, 100434 (2021), ACS Appl. Nano Mater. 6, 646 (2023), ACS Appl. Polym. Mater. 3, 3649 (2021)). AIE molecules, as novel luminescent materials, provide a new tool for real-time and in-situ study of polymer structures during fluorescence imaging. Currently, existing techniques incorporate AIE molecules as luminescent dyes into photoresist systems to impart fluorescence to the polymerized structures (CN 120588485 A). However, in these methods, AIE molecules exist only as a dopant fluorescent component. There are no reports in existing literature or patents regarding whether AIE molecules can directly participate in two-photon photopolymerization and function as photosensitizers. Summary of the Invention

[0004] To address the problems of high resolution, uneven light emission, and complex material composition in the manufacturing process of existing light-emitting functional devices, the first objective of this invention is to provide a photosensitive material that can be used as a photosensitizer by aggregation-induced emission dyes. By using aggregation-induced emission dyes to combine the properties of photosensitizer and light emission, light-emitting functional devices can be manufactured. First, the aggregation-induced emission dyes act as photosensitizers to induce monomer polymerization to manufacture micro-nano structures. Second, the aggregation-induced emission dyes are present in the polymerized micro-nano structures, giving the structures excellent fluorescence properties.

[0005] The second objective of this invention is to provide a method for preparing a photosensitive material in which aggregation-induced emission dyes can be used as photosensitizers. This method has the advantages of simple process flow, low cost, and good reproducibility, making it suitable for large-scale preparation and practical applications.

[0006] To achieve the above-mentioned technical objectives, the technical solution of the present invention is as follows: This invention provides a photosensitive material composed of a monomer and an aggregation-induced luminescent dye, wherein the monomer is an olefinic unsaturated free radical photopolymerizable monomer.

[0007] By using aggregation-induced emission dyes as photosensitizers, monomer polymerization can be induced under laser irradiation to create microstructures; The fluorescent properties of aggregation-induced emission dyes are used to create structures with fluorescent properties.

[0008] Under the action of a laser, aggregation-induced emission dyes induce the olefinic unsaturated bonds (such as C=C) in monomer molecules to break and transform into carbon-carbon single bonds (CC), thereby completing monomer polymerization.

[0009] Preferably, based on the relative mass fraction of each component in the photosensitive material, the monomer is 94%-99.8% and the aggregation-induced emission dye is 0.2%-6%.

[0010] Preferably, the olefinic unsaturated free radical photopolymerizable monomer is a (meth)acrylate monomer.

[0011] As an example, the (meth)acrylate monomers are selected from one or more mixtures of tetrahydrofurfuryl acrylate, 1,6-hexanediol diacrylate, trimethylolpropane triacrylate, di-trimethylolpropane tetraacrylate, tri(2-hydroxyethyl)isocyanurate triacrylate, pentaerythritol tetraacrylate, and dipentaerythritol penta / hexaacrylate.

[0012] Preferably, the aggregation-induced emission dye comprises a core vinyl structural unit, and at least one rotatable aromatic group is attached to at least one carbon atom of the vinyl structural unit. More preferably, the aggregation-induced emission dye is selected from one or more of diphenylethylene and its derivatives, tetraphenylethylene and its derivatives, cyano-substituted ethylene derivatives, and stilbeneyl anthracene derivatives. Wherein, "derivative" refers to a compound in which the hydrogen atom on the aromatic ring of the corresponding parent compound is replaced by a substituent, and the substituent is selected from the group consisting of halogens, C1-C6 alkyl groups, C1-C6 alkoxy groups, amino groups, nitro groups, and cyano groups. For example, the tetraphenylethylene derivative is selected from tetramethoxytetraphenylene, tetraacrylate tetraphenylene, etc.

[0013] This invention provides a method for preparing a photosensitive material, characterized in that the method includes the following steps: mixing a monomer and an aggregation-induced emission dye uniformly with a solvent; and then removing the solvent from the solution to form a photosensitive material.

[0014] The present invention also provides a laser direct writing method, which includes the following steps: (1) taking a photosensitive material as described in any one of claims 1-6 and placing it in a closed cavity; (2) placing the closed cavity containing the photosensitive material on the displacement stage of an optical system; activating the optical system, wherein the optical system emits a laser beam toward the photosensitive material and irradiates the photosensitive material according to a preset moving trajectory, so that the photosensitive material aggregates along the scanning path of the light source; (3) washing away the unaggregated photosensitive material; (4) drying to obtain the aggregated micro / nano structure.

[0015] As an example, the laser beam in the optical system includes one or more combinations of pulsed lasers and continuous lasers.

[0016] The laser direct writing method can be used to manufacture three-dimensional micro and nanostructures and can be applied to fields such as 3D printing, photolithography, or optical storage.

[0017] In the laser direct writing method, the photosensitive material undergoes a polymerization reaction through a two-photon absorption effect.

[0018] In this invention, the degree of polymerization of the photosensitive material exhibits a non-linear increasing trend with the intensity of the laser power. The fluorescence intensity of the micro / nano structure after polymerization of the photosensitive material also exhibits a non-linear increasing trend with the intensity of the laser power.

[0019] The present invention also provides a device comprising a three-dimensional micro / nano structure formed from the aforementioned photosensitive material using a laser direct-writing method. As an example, the device is a light-emitting device.

[0020] Compared with the prior art, the present invention has the following beneficial effects: (1) The present invention discovers that, in the absence of any other initiators and photosensitizers, aggregation-induced luminescent dyes can act as photosensitizers without any chemical modification, and induce the polymerization of acrylate monomers under the action of laser.

[0021] (2) This invention provides a simple and low-cost method for preparing photosensitive materials. In this system, the aggregation-induced emission dye has both photosensitizing and luminescent properties. First, the aggregation-induced emission dye acts as a photosensitizer to induce the polymerization of monomers to create high-precision micro-nano structures, which have the characteristics of high resolution, low excitation power and low cost. Second, the aggregation-induced emission dye exists in the polymerized micro-nano structures, giving the structures excellent fluorescence properties.

[0022] (3) The photosensitive material and its preparation method, as well as the laser direct writing method provided by the present invention, which uses aggregated luminescent dye as a photosensitizer, are also applicable to 3D printing, photolithography or optical storage. Attached Figure Description

[0023] The accompanying drawings, which are included to provide a further understanding of the invention and form part of this invention, illustrate exemplary embodiments of the invention and are used to explain the invention, but do not constitute an undue limitation of the invention. In the drawings: Figure 1 This is a schematic flowchart of the preparation method of a photosensitive material according to an embodiment of the present invention; Figure 2 This is a schematic flowchart of the laser direct writing method according to an embodiment of the present invention; Figure 3 This is a schematic diagram of the laser processing of the photosensitive material of the present invention; Figure 4 This is a graph showing the relationship between the feature dimensions of the material manufacturing line structure in Embodiment 1 of the present invention and the laser power, along with the corresponding SEM image. Figure 5 This is a 3µm three-dimensional structure fabricated with the material in Embodiment 1 of the present invention at a laser power of 1mw, and a partially enlarged view of the structure. Figure 6 This is a graph showing the Raman spectral changes of the sample before and after polymerization and the relationship between the conversion degree of the C=C double bond and the laser power in the corresponding embodiment 1 of the present invention. Figure 7 These are fluorescence characterization images of the photosensitive material in its liquid and polymerized states in Example 1 of this invention; Figure 8 These are bright-field and fluorescence field images of the structure manufactured using the material in Embodiment 1 of the present invention, observed under a fluorescence microscope, as well as a 3D structure diagram obtained based on fluorescence signal reconstruction. Detailed Implementation

[0024] The technical solutions of the embodiments of the present invention will be clearly and completely described below with reference to the accompanying drawings. Obviously, the described embodiments are only some, not all, of the embodiments of the present invention. Based on the embodiments of the present invention, all other embodiments obtained by those skilled in the art without creative effort are within the scope of protection of the present invention.

[0025] The photosensitive material of this invention possesses excellent two-photon absorption capability, enabling it to absorb two photons in a very short time, thereby triggering the polymerization reaction of the monomer. The two-photon absorption process is related to the square of the photon density and is a nonlinear absorption process. During two-photon lithography, the reaction only occurs in the laser focal region; therefore, the photosensitive material prepared by this invention can achieve a processing precision at the hundred-nanometer level. Simultaneously, because the aggregated luminescent dye is present in the polymerized structure, the structure also possesses good luminescent properties. The preparation method of this invention is simple and low-cost, and the structures prepared using the photosensitive material of this invention can be used in fields such as luminescent functional devices and biomedicine.

[0026] Example 1 In this embodiment, the monomer in the photosensitive material is dipentaerythritol penta / hexaacrylate, and the aggregation-induced emission dye is tetraphenylethylene. The mass percentages of the monomer and the aggregation-induced emission dye are shown in Table 1.

[0027] Please see Figure 1 Figure 1 is a schematic flowchart of the preparation method of the photosensitive material in this embodiment. As shown in the figure, the preparation method of the photosensitive material in this embodiment is used to achieve structure manufacturing with a resolution of hundreds of nanometers. The preparation method of the photosensitive material includes the following steps S1 to S3. In step 1, monomers and aggregation-induced emission dyes are weighed in proportion. In step S2, acetone is added and mixed evenly with the monomers and aggregation-induced emission dyes to form a uniformly mixed solution. In this embodiment, acetone is added to the weighed monomers and aggregation-induced emission dyes, shaken to mix them, and then ultrasonically vibrated to completely disperse the monomers and aggregation-induced emission dyes in the acetone to form a uniformly mixed solution. In step 3, the acetone is removed by baking to form the photosensitive material. In this embodiment, the uniformly mixed solution is placed in an oven and baked at 60°C for 12 hours until the acetone in the solution is completely removed, thus obtaining the photosensitive material in which the aggregation-induced emission dye is used as a photosensitizer.

[0028] Please see Figure 2 This is a schematic flowchart of the laser direct writing method in this embodiment; the laser direct writing method in this embodiment includes steps S01 to S03. In step S01, the prepared photosensitive material is encapsulated in a sealed cavity with a glass slide as the substrate and a glass slide as the cover plate. In step S02, the photosensitive material is placed on the displacement stage of the optical system, and then the laser is activated, with the laser device emitting a laser beam towards the sample. By controlling the displacement stage to move the sample according to a preset trajectory, the sample is three-dimensionally processed. This embodiment achieves nanoscale processing of the material by adjusting processing parameters such as laser power and scanning speed. In step S03, the cover glass slide is removed from the sample after laser treatment, and the unpolymerized photosensitive material is washed away; after drying, the polymerized micro / nano structure is obtained. Please refer to... Figure 3 , Figure 3 This is a laser processing technique based on direct laser writing to fabricate photosensitive materials. A laser beam is focused inside the material through a high numerical aperture oil immersion objective (100×, NA 1.4). A displacement stage is used to position and scan the sample, constructing a three-dimensional structure layer by layer from bottom to top. Table 1 shows the minimum threshold power and characteristic dimensions of the fabricated structures at different mass fractions of monomers and aggregation-induced emission dyes.

[0029] Table 1 Please see Figure 4 , Figure 4 This is a typical SEM image of the linear structure fabricated using the photosensitive material in Example 1, and a typical graph showing the relationship between its feature size and laser power. This data is from the formulation (DPHA / TPE = 98.5 / 1.5). Data analysis shows that the structural feature size exhibits a non-linear positive correlation with laser power. Please refer to... Figure 5 , Figure 5 The image shows a 3µm high three-dimensional structure fabricated using the photosensitive material in Example 1 at a laser power of 1mw, along with a magnified view of the structure. This data is derived from the formulation (DPHA / TPE=98.5 / 1.5).

[0030] Please see Figure 6 The figure shows the Raman spectral density changes of the photosensitive material sample before and after polymerization in Example 1, as well as the relationship between the conversion rate of the C=C double bond and the laser power. As shown in the figure, in this embodiment, the peak value of the C=C double bond in the photosensitive material before and after polymerization is significantly different. Because the carbon-carbon double bond breaks during polymerization, the Raman peak of the C=C double bond after polymerization is significantly reduced. Simultaneously, Raman spectral density tests were performed on samples under different laser powers. The conversion rate, calculated from the Raman peak area, shows a non-linear increasing trend with laser power. In other words, in this embodiment, as the laser power increases, the conversion rate of the C=C bond to the C=C single bond in the photosensitive material increases. The conversion rate can quantify the degree of polymerization; generally, a high conversion rate corresponds to a high degree of polymerization. Therefore, in other words, as the laser power increases, the degree of polymerization of the photosensitive material tends to increase. Please see Figure 7The figure shows the fluorescence characterization of the photosensitive material and the structure etched at different powers in Example 1. This data comes from the formulation (DPHA / TPE = 98.5 / 1.5). As shown in the figure, in this embodiment, the fluorescence intensity of the photosensitive material sample and the laser power exhibit a non-linear growth trend. In other words, this embodiment can control the fluorescence intensity of the structure fabricated from the photosensitive material by changing the laser power. Within a certain range, as the laser power increases, the degree of material aggregation increases, and the aggregation-induced emission dye exhibits a non-linear growth trend in fluorescence intensity due to its restricted intramolecular movement.

[0031] Please see Figure 8 The figures show bright-field and fluorescence field images of the structure fabricated using the photosensitive material in Example 1, as well as a 3D structure image reconstructed based on the fluorescence signal, observed under a fluorescence microscope. As shown, in this method, the fabricated structure has a clear outline and complete boundaries. Furthermore, the fluorescence field images and 3D reconstruction results demonstrate that the prepared structure exhibits uniform fluorescence characteristics, without significant fluctuations in fluorescence intensity, dark areas, or localized fluorescence quenching. This indicates that the material prepared in this invention possesses good polymerization uniformity and structural integrity during the polymerization process. This uniform fluorescence response enables in-situ fluorescence characterization and 3D visualization reconstruction of the microstructure.

[0032] Example 2 In this embodiment, the monomer in the photosensitive material is dipentaerythritol penta / hexaacrylate, and the aggregation-induced emission dye is tetramethoxytetraphenylene. The mass percentages of the monomer and the aggregation-induced emission dye are shown in Table 2.

[0033] Please see Figure 1 Figure 1 is a schematic flowchart illustrating the preparation method of the photosensitive material in this embodiment. As shown, the preparation method of the photosensitive material in this embodiment is used to achieve structure fabrication with a resolution of hundreds of nanometers. The preparation method of the photosensitive material includes the following steps S1 to S3. In step 1, monomers and aggregation-induced emission dyes are weighed in proportion. In step S2, acetone is added and mixed evenly with the monomers and aggregation-induced emission dyes to form a uniformly mixed solution. In this embodiment, acetone is added to the weighed monomers and aggregation-induced emission dyes, shaken to mix, and then ultrasonically vibrated to completely disperse the monomers and aggregation-induced emission dyes in the acetone to form a uniformly mixed solution. In step 3, the acetone is removed by baking to form the photosensitive material. In this embodiment, the uniformly mixed solution is placed in an oven and baked at 60°C for 12 hours until the acetone in the solution is completely removed, thus obtaining the photosensitive material.

[0034] Please see Figure 2This is a schematic flowchart of the laser direct writing method in this embodiment; the laser direct writing method in this embodiment includes steps S01 to S03. In step S01, the prepared photosensitive material is encapsulated in a sealed cavity with a glass slide as the substrate and a glass slide as the cover plate. In step S02, the photosensitive material is placed on the displacement stage of the optical system, and then the laser is activated, with the laser device emitting a laser beam towards the sample. By controlling the displacement stage to move the sample according to a preset trajectory, the sample is three-dimensionally processed. This embodiment achieves nanoscale processing of the material by adjusting processing parameters such as laser power and scanning speed. In step S03, the cover glass slide is removed from the sample after laser treatment, and the unpolymerized photosensitive material is washed away; after drying, the polymerized micro / nano structure is obtained. Please refer to... Figure 3 , Figure 3 This is a laser processing technique based on direct laser writing to fabricate photosensitive materials. A laser beam is focused inside the material through a high numerical aperture oil immersion objective (100×, NA 1.4). A displacement stage is used to position and scan the sample, constructing a three-dimensional structure layer by layer from bottom to top. Table 2 shows the minimum threshold power and characteristic dimensions of the fabricated structures at different mass fractions of monomers and aggregation-induced emission dyes.

[0035] Table 2 Example 3 In this embodiment, the monomer in the photosensitive material is dipentaerythritol penta / hexaacrylate, and the aggregation-induced emission dye is tetrabutylene tetraacrylate. The mass percentages of the monomer and the aggregation-induced emission dye are shown in Table 3.

[0036] Please see Figure 1 Figure 1 is a schematic flowchart illustrating the preparation method of the photosensitive material in this embodiment. As shown, the preparation method of the photosensitive material in this embodiment is used to achieve structure fabrication with a resolution of hundreds of nanometers. The preparation method of the photosensitive material includes the following steps S1 to S3. In step 1, monomers and aggregation-induced emission dyes are weighed in proportion. In step S2, acetone is added and mixed evenly with the monomers and aggregation-induced emission dyes to form a uniformly mixed solution. In this embodiment, acetone is added to the weighed monomers and aggregation-induced emission dyes, shaken to mix, and then ultrasonically vibrated to completely disperse the monomers and aggregation-induced emission dyes in the acetone to form a uniformly mixed solution. In step 3, the acetone is removed by baking to form the photosensitive material. In this embodiment, the uniformly mixed solution is placed in an oven and baked at 60°C for 12 hours until the acetone in the solution is completely removed, thus obtaining the photosensitive material.

[0037] Please see Figure 2This is a schematic flowchart of the laser direct writing method in this embodiment; the laser direct writing method in this embodiment includes steps S01 to S03. In step S01, the prepared photosensitive material is encapsulated in a sealed cavity with a glass slide as the substrate and a glass slide as the cover plate. In step S02, the photosensitive material is placed on the displacement stage of the optical system, and then the laser is activated, with the laser device emitting a laser beam towards the sample. By controlling the displacement stage to move the sample according to a preset trajectory, the sample is three-dimensionally processed. This embodiment achieves nanoscale processing of the material by adjusting processing parameters such as laser power and scanning speed. In step S03, the cover glass slide is removed from the sample after laser treatment, and the unpolymerized photosensitive material is washed away; after drying, the polymerized micro / nano structure is obtained. Please refer to... Figure 3 , Figure 3 This is a laser processing technique based on direct laser writing to fabricate photosensitive materials. A laser beam is focused inside the material through a high numerical aperture oil immersion objective (100×, NA 1.4). A displacement stage is used to position and scan the sample, constructing a three-dimensional structure layer by layer from bottom to top. Table 3 shows the minimum threshold power and characteristic dimensions of the fabricated structures at different mass fractions of monomers and aggregation-induced emission dyes.

[0038] Table 3 Example 4 In this embodiment, the monomer in the photosensitive material is dipentaerythritol penta / hexaacrylate, and the aggregation-induced emission dye is triphenylamine-dicyanoethylene. The mass percentages of the monomer and the aggregation-induced emission dye are shown in Table 4.

[0039] Please see Figure 1 Figure 1 is a schematic flowchart illustrating the preparation method of the photosensitive material in this embodiment. As shown, the preparation method of the photosensitive material in this embodiment is used to achieve structure fabrication with a resolution of hundreds of nanometers. The preparation method of the photosensitive material includes the following steps S1 to S3. In step 1, monomers and aggregation-induced emission dyes are weighed in proportion. In step S2, acetone is added and mixed evenly with the monomers and aggregation-induced emission dyes to form a uniformly mixed solution. In this embodiment, acetone is added to the weighed monomers and aggregation-induced emission dyes, shaken to mix, and then ultrasonically vibrated to completely disperse the monomers and aggregation-induced emission dyes in the acetone to form a uniformly mixed solution. In step 3, the acetone is removed by baking to form the photosensitive material. In this embodiment, the uniformly mixed solution is placed in an oven and baked at 60°C for 12 hours until the acetone in the solution is completely removed, thus obtaining the photosensitive material.

[0040] Please see Figure 2This is a schematic flowchart of the laser direct writing method in this embodiment; the laser direct writing method in this embodiment includes steps S01 to S03. In step S01, the prepared photosensitive material is encapsulated in a sealed cavity with a glass slide as the substrate and a glass slide as the cover plate. In step S02, the photosensitive material is placed on the displacement stage of the optical system, and then the laser is activated, with the laser device emitting a laser beam towards the sample. By controlling the displacement stage to move the sample according to a preset trajectory, the sample is three-dimensionally processed. This embodiment achieves nanoscale processing of the material by adjusting processing parameters such as laser power and scanning speed. In step S03, the cover glass slide is removed from the sample after laser treatment, and the unpolymerized photosensitive material is washed away; after drying, the polymerized micro / nano structure is obtained. Please refer to... Figure 3 , Figure 3 This is a laser processing technique based on direct laser writing to fabricate photosensitive materials. A laser beam is focused inside the material through a high numerical aperture oil immersion objective (100×, NA 1.4). A displacement stage is used to position and scan the sample, constructing a three-dimensional structure layer by layer from bottom to top. Table 4 shows the minimum threshold power and characteristic dimensions of the fabricated structures at different monomer and aggregation-induced emission dye mass fraction ratios.

[0041] Table 4 Example 5 In this embodiment, the monomer in the photosensitive material is dipentaerythritol penta / hexaacrylate, and the aggregation-induced emission dye is carbazole-dicyanoethylene. The mass percentages of the monomer and the aggregation-induced emission dye are shown in Table 5.

[0042] Please see Figure 1 Figure 1 is a schematic flowchart illustrating the preparation method of the photosensitive material in this embodiment. As shown, the preparation method of the photosensitive material in this embodiment is used to achieve structure fabrication with a resolution of hundreds of nanometers. The preparation method of the photosensitive material includes the following steps S1 to S3. In step 1, monomers and aggregation-induced emission dyes are weighed in proportion. In step S2, acetone is added and mixed evenly with the monomers and aggregation-induced emission dyes to form a uniformly mixed solution. In this embodiment, acetone is added to the weighed monomers and aggregation-induced emission dyes, shaken to mix, and then ultrasonically vibrated to completely disperse the monomers and aggregation-induced emission dyes in the acetone to form a uniformly mixed solution. In step 3, the acetone is removed by baking to form the photosensitive material. In this embodiment, the uniformly mixed solution is placed in an oven and baked at 60°C for 12 hours until the acetone in the solution is completely removed, thus obtaining the photosensitive material.

[0043] Please see Figure 2This is a schematic flowchart of the laser direct writing method in this embodiment; the laser direct writing method in this embodiment includes steps S01 to S03. In step S01, the prepared photosensitive material is encapsulated in a sealed cavity with a glass slide as the substrate and a glass slide as the cover plate. In step S02, the photosensitive material is placed on the displacement stage of the optical system, and then the laser is activated, with the laser device emitting a laser beam towards the sample. By controlling the displacement stage to move the sample according to a preset trajectory, the sample is three-dimensionally processed. This embodiment achieves nanoscale processing of the material by adjusting processing parameters such as laser power and scanning speed. In step S03, the cover glass slide is removed from the sample after laser treatment, and the unpolymerized photosensitive material is washed away; after drying, the polymerized micro / nano structure is obtained. Please refer to... Figure 3 , Figure 3 This is a laser processing technique based on direct laser writing to fabricate photosensitive materials. A laser beam is focused inside the material through a high numerical aperture oil immersion objective (100×, NA 1.4). A displacement stage is used to position and scan the sample, constructing a three-dimensional structure layer by layer from bottom to top. Table 5 shows the minimum threshold power and characteristic dimensions of the fabricated structures at different mass fractions of monomers and aggregation-induced emission dyes.

[0044] Table 5 Example 6 In this embodiment, the monomer in the photosensitive material is dipentaerythritol penta / hexaacrylate, and the aggregation-induced emission dye is stilbene. The mass percentages of the monomer and the aggregation-induced emission dye are shown in Table 6.

[0045] Please see Figure 1 Figure 1 is a schematic flowchart illustrating the preparation method of the photosensitive material in this embodiment. As shown, the preparation method of the photosensitive material in this embodiment is used to achieve structure fabrication with a resolution of hundreds of nanometers. The preparation method of the photosensitive material includes the following steps S1 to S3. In step 1, monomers and aggregation-induced emission dyes are weighed in proportion. In step S2, acetone is added and mixed evenly with the monomers and aggregation-induced emission dyes to form a uniformly mixed solution. In this embodiment, acetone is added to the weighed monomers and aggregation-induced emission dyes, shaken to mix, and then ultrasonically vibrated to completely disperse the monomers and aggregation-induced emission dyes in the acetone to form a uniformly mixed solution. In step 3, the acetone is removed by baking to form the photosensitive material. In this embodiment, the uniformly mixed solution is placed in an oven and baked at 60°C for 12 hours until the acetone in the solution is completely removed, thus obtaining the photosensitive material.

[0046] Please see Figure 2This is a schematic flowchart of the laser direct writing method in this embodiment; the laser direct writing method in this embodiment includes steps S01 to S03. In step S01, the prepared photosensitive material is encapsulated in a sealed cavity with a glass slide as the substrate and a glass slide as the cover plate. In step S02, the photosensitive material is placed on the displacement stage of the optical system, and then the laser is activated, with the laser device emitting a laser beam towards the sample. By controlling the displacement stage to move the sample according to a preset trajectory, the sample is three-dimensionally processed. This embodiment achieves nanoscale processing of the material by adjusting processing parameters such as laser power and scanning speed. In step S03, the cover glass slide is removed from the sample after laser treatment, and the unpolymerized photosensitive material is washed away; after drying, the polymerized micro / nano structure is obtained. Please refer to... Figure 3 , Figure 3 This is a laser processing technique based on direct laser writing to fabricate photosensitive materials. A laser beam is focused inside the material through a high numerical aperture oil immersion objective (100×, NA 1.4). A displacement stage is used to position and scan the sample, constructing a three-dimensional structure layer by layer from bottom to top. Table 6 shows the minimum threshold power and characteristic dimensions of the fabricated structures at different mass fractions of monomers and aggregation-induced emission dyes.

[0047] Table 6 Example 7 In this embodiment, the monomer in the photosensitive material is dipentaerythritol penta / hexaacrylate, and the aggregation-induced emission dye is 9,10-bis[(E)-4-methoxystyryl]anthracene. The mass percentages of the monomer and the aggregation-induced emission dye are shown in Table 7.

[0048] Please see Figure 1 Figure 1 is a schematic flowchart illustrating the preparation method of the photosensitive material in this embodiment. As shown, the preparation method of the photosensitive material in this embodiment is used to achieve structure fabrication with a resolution of hundreds of nanometers. The preparation method of the photosensitive material includes the following steps S1 to S3. In step 1, monomers and aggregation-induced emission dyes are weighed in proportion. In step S2, acetone is added and mixed evenly with the monomers and aggregation-induced emission dyes to form a uniformly mixed solution. In this embodiment, acetone is added to the weighed monomers and aggregation-induced emission dyes, shaken to mix, and then ultrasonically vibrated to completely disperse the monomers and aggregation-induced emission dyes in the acetone to form a uniformly mixed solution. In step 3, the acetone is removed by baking to form the photosensitive material. In this embodiment, the uniformly mixed solution is placed in an oven and baked at 60°C for 12 hours until the acetone in the solution is completely removed, thus obtaining the photosensitive material.

[0049] Please see Figure 2This is a schematic flowchart of the laser direct writing method in this embodiment; the laser direct writing method in this embodiment includes steps S01 to S03. In step S01, the prepared photosensitive material is encapsulated in a sealed cavity with a glass slide as the substrate and a glass slide as the cover plate. In step S02, the photosensitive material is placed on the displacement stage of the optical system, and then the laser is activated, with the laser device emitting a laser beam towards the sample. By controlling the displacement stage to move the sample according to a preset trajectory, the sample is three-dimensionally processed. This embodiment achieves nanoscale processing of the material by adjusting processing parameters such as laser power and scanning speed. In step S03, the cover glass slide is removed from the sample after laser treatment, and the unpolymerized photosensitive material is washed away; after drying, the polymerized micro / nano structure is obtained. Please refer to... Figure 3 , Figure 3 This is a laser processing technique based on direct laser writing to fabricate photosensitive materials. A laser beam is focused inside the material through a high numerical aperture oil immersion objective (100×, NA 1.4). A displacement stage is used to position and scan the sample, constructing a three-dimensional structure layer by layer from bottom to top. Table 7 shows the minimum threshold power and characteristic dimensions of the fabricated structures at different mass fractions of monomers and aggregation-induced emission dyes.

[0050] Table 7 Example 8 In this embodiment, the monomer in the photosensitive material is 1,6-hexanediol diacrylate, and the aggregation-induced emission dye is tetraphenylethylene. The mass percentages of the monomer and the aggregation-induced emission dye are shown in Table 8.

[0051] Please see Figure 1 Figure 1 is a schematic flowchart illustrating the preparation method of the photosensitive material in this embodiment. As shown, the preparation method of the photosensitive material in this embodiment is used to achieve structure fabrication with a resolution of hundreds of nanometers. The preparation method of the photosensitive material includes the following steps S1 to S3. In step 1, monomers and aggregation-induced emission dyes are weighed in proportion. In step S2, acetone is added and mixed evenly with the monomers and aggregation-induced emission dyes to form a uniformly mixed solution. In this embodiment, acetone is added to the weighed monomers and aggregation-induced emission dyes, shaken to mix, and then ultrasonically vibrated to completely disperse the monomers and aggregation-induced emission dyes in the acetone to form a uniformly mixed solution. In step 3, the acetone is removed by baking to form the photosensitive material. In this embodiment, the uniformly mixed solution is placed in an oven and baked at 60°C for 12 hours until the acetone in the solution is completely removed, thus obtaining the photosensitive material.

[0052] Please see Figure 2This is a schematic flowchart of the laser direct writing method in this embodiment; the laser direct writing method in this embodiment includes steps S01 to S03. In step S01, the prepared photosensitive material is encapsulated in a sealed cavity with a glass slide as the substrate and a glass slide as the cover plate. In step S02, the photosensitive material is placed on the displacement stage of the optical system, and then the laser is activated, with the laser device emitting a laser beam towards the sample. By controlling the displacement stage to move the sample according to a preset trajectory, the sample is three-dimensionally processed. This embodiment achieves nanoscale processing of the material by adjusting processing parameters such as laser power and scanning speed. In step S03, the cover glass slide is removed from the sample after laser treatment, and the unpolymerized photosensitive material is washed away; after drying, the polymerized micro / nano structure is obtained. Please refer to... Figure 3 , Figure 3 This is a laser processing technique based on direct laser writing to fabricate photosensitive materials. A laser beam is focused inside the material through a high numerical aperture oil immersion objective (100×, NA 1.4). A displacement stage is used to position and scan the sample, constructing a three-dimensional structure layer by layer from bottom to top. Table 8 shows the minimum threshold power and characteristic dimensions of the fabricated structures at different mass fractions of monomers and aggregation-induced emission dyes.

[0053] Table 8 Example 9 In this embodiment, the monomer in the photosensitive material is pentaerythritol tetraacrylate, and the aggregation-induced emission dye is tetraphenylethylene. The mass percentages of the monomer and the aggregation-induced emission dye are shown in Table 9.

[0054] Please see Figure 1 Figure 1 is a schematic flowchart illustrating the preparation method of the photosensitive material in this embodiment. As shown, the preparation method of the photosensitive material in this embodiment is used to achieve structure fabrication with a resolution of hundreds of nanometers. The preparation method of the photosensitive material includes the following steps S1 to S3. In step 1, monomers and aggregation-induced emission dyes are weighed in proportion. In step S2, acetone is added and mixed evenly with the monomers and aggregation-induced emission dyes to form a uniformly mixed solution. In this embodiment, acetone is added to the weighed monomers and aggregation-induced emission dyes, shaken to mix, and then ultrasonically vibrated to completely disperse the monomers and aggregation-induced emission dyes in the acetone to form a uniformly mixed solution. In step 3, the acetone is removed by baking to form the photosensitive material. In this embodiment, the uniformly mixed solution is placed in an oven and baked at 60°C for 12 hours until the acetone in the solution is completely removed, thus obtaining the photosensitive material.

[0055] Please see Figure 2This is a schematic flowchart of the laser direct writing method in this embodiment; the laser direct writing method in this embodiment includes steps S01 to S03. In step S01, the prepared photosensitive material is encapsulated in a sealed cavity with a glass slide as the substrate and a glass slide as the cover plate. In step S02, the photosensitive material is placed on the displacement stage of the optical system, and then the laser is activated, with the laser device emitting a laser beam towards the sample. By controlling the displacement stage to move the sample according to a preset trajectory, the sample is three-dimensionally processed. This embodiment achieves nanoscale processing of the material by adjusting processing parameters such as laser power and scanning speed. In step S03, the cover glass slide is removed from the sample after laser treatment, and the unpolymerized photosensitive material is washed away; after drying, the polymerized micro / nano structure is obtained. Please refer to... Figure 3 , Figure 3 This is a laser processing technique based on direct laser writing to fabricate photosensitive materials. A laser beam is focused inside the material through a high numerical aperture oil immersion objective (100×, NA 1.4). A displacement stage is used to position and scan the sample, constructing a three-dimensional structure layer by layer from bottom to top. Table 9 shows the minimum threshold power and characteristic dimensions of the fabricated structures at different mass fractions of monomers and aggregation-induced emission dyes.

[0056] Table 9 In summary, this invention provides a photosensitive material, a preparation method based on this material, and a laser direct-writing method. This invention involves mixing a monomer and an aggregation-induced emission dye in a specific ratio, then mixing them uniformly with acetone, and finally drying the acetone to form a two-photon material in which the aggregation-induced emission dye serves as an initiator. The photosensitive material prepared in this way can achieve a processing precision at the hundred-nanometer level, while the processed structure also exhibits good luminescent properties. The preparation method of this invention is simple and low-cost, and the laser direct-writing technology has advantages such as non-contact, high precision, and easy integration. Structures prepared using the two-photon material of this invention can be used in luminescent functional devices, biomedicine, and other fields.

[0057] The embodiments described above are merely illustrative of implementation methods of the present invention, and while the descriptions are specific and detailed, they should not be construed as limiting the scope of the invention. It should be noted that those skilled in the art can make various modifications and improvements without departing from the concept of the present invention, and these modifications and improvements all fall within the scope of protection of the present invention. Therefore, the scope of protection of this invention should be determined by the appended claims.

Claims

1. A photosensitive material, characterized in that, It consists of a monomer and an aggregation-induced luminescent dye, wherein the monomer is an olefinic unsaturated free radical photopolymerizable monomer.

2. The photosensitive material according to claim 1, characterized in that, Based on the relative mass fraction of each component in the photosensitive material, the monomer accounts for 94%-99.8%, and the aggregation-induced emission dye accounts for 0.2%-6%.

3. The photosensitive material according to claim 1, characterized in that, The olefinic unsaturated free radical photopolymerizable monomer is a (meth)acrylate monomer.

4. The photosensitive material according to claim 3, characterized in that, The (meth)acrylate monomers are selected from one or more mixtures of tetrahydrofurfuryl acrylate, 1,6-hexanediol diacrylate, trimethylolpropane triacrylate, di-trimethylolpropane tetraacrylate, tri(2-hydroxyethyl)isocyanurate triacrylate, pentaerythritol tetraacrylate, and dipentaerythritol penta / hexaacrylate.

5. The photosensitive material according to claim 1, characterized in that, The aggregation-induced emission dye comprises a core vinyl structural unit, and at least one freely rotatable aromatic group is attached to at least one carbon atom of the vinyl structural unit.

6. The photosensitive material according to claim 5, characterized in that, The aggregation-induced emission dye is selected from one or a mixture of multiple types of diphenylethylene and its derivatives, tetraphenylethylene and its derivatives, cyano-substituted ethylene derivatives, and stilbene anthracene derivatives.

7. The method for preparing the photosensitive material according to any one of claims 1-6, characterized in that, The steps include: mixing the monomer and the aggregation-induced emission dye evenly with a solvent; Then the solvent in the solution is removed to form a photosensitive material.

8. A laser direct writing method, characterized in that, Includes the following steps: (1) Take the photosensitive material as described in any one of claims 1-6 and place it in a closed cavity; (2) Place the enclosed cavity containing the photosensitive material on the displacement stage of the optical system; start the optical system, and the optical system emits a laser beam toward the photosensitive material, irradiating the photosensitive material according to a preset moving trajectory, so that the photosensitive material aggregates along the scanning path of the light source; (3) Wash away the unpolymerized photosensitive material. (4) Drying to obtain the polymerized micro / nano structure.

9. The laser direct writing method according to claim 8, characterized in that, The laser beam in the optical system includes one or more combinations of pulsed lasers and continuous lasers.

10. The laser direct writing method according to claim 8, characterized in that, The method is used to manufacture three-dimensional micro / nano structures and can be applied in the fields of 3D printing, photolithography, or optical storage.

11. The laser direct writing method according to claim 8, characterized in that, The photosensitive material undergoes a polymerization reaction through a two-photon absorption effect; the degree of polymerization of the photosensitive material increases non-linearly with the intensity of the laser power; the fluorescence intensity of the micro / nano structure after polymerization of the photosensitive material increases non-linearly with the intensity of the laser power.

12. A device, characterized in that, The device comprises a three-dimensional micro / nano structure formed by laser direct writing of the photosensitive material according to any one of claims 1 to 6.

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