Luminescent organic gel with surface modified by single-layer silicon dioxide photonic crystal and preparation method thereof
By constructing a monolayer silica photonic crystal on a PDMS substrate and combining it with a photocuring precursor solution, the problem of stable construction of photonic crystals on water-soluble luminescent gel substrates was solved, achieving efficient photonic crystal integration and significantly improving light output efficiency and device performance.
Patent Information
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- UNIV OF JINAN
- Filing Date
- 2026-01-27
- Publication Date
- 2026-05-01
AI Technical Summary
Existing technologies struggle to stably construct monolayer photonic crystal structures on water-soluble luminescent organic gel substrates, primarily because spin coating and gas/liquid interface transfer methods can lead to gel dissolution or structural damage, making them unsuitable for water-sensitive substrates.
Using a PDMS substrate as a carrier, a monolayer of silica photonic crystal is formed on its surface, and a luminescent organic gel is formed through a photocuring precursor solution (isopentyltriphenylphosphine bromide, manganese bromide, 1-vinyl-2-pyrrolidone and 1-hydroxycyclohexylphenyl ketone), avoiding dissolution or swelling under aqueous conditions, and combining low-temperature dry transfer and photocuring interface anchoring technology.
The controllable fabrication of large-area, high-intensity monolayer photonic crystals on the surface of luminescent organic gels has been achieved, enhancing the light output efficiency by more than 60%, improving the signal-to-noise ratio and detection sensitivity of the device, and avoiding high-temperature processing and strong chemical corrosion steps.
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Abstract
Description
A luminescent organogel with surface-modified monolayer silica photonic crystal and its preparation method Technical Field
[0001] This invention relates to the field of photonic crystal technology, specifically to a luminescent organic gel with a surface-modified monolayer silica photonic crystal and its preparation method. Background Technology
[0002] The fabrication of monolayer silica photonic crystals typically relies on rigid, non-luminescent, and solvent-resistant substrate materials (such as silicon wafers, glass, or specific polymers), primarily employing spin-coating-self-assembly methods or gas / liquid interface self-assembly transfer methods. Spin-coating involves high-speed rotation of the substrate, causing a suspension of aqueous or alcohol-based silica microspheres to self-assemble into an ordered monolayer structure during solvent evaporation. Gas / liquid interface methods rely on the microspheres self-assembling into a film on a water surface or liquid / liquid interface, which is then transferred to a rigid substrate surface. Both methods require substrates with high mechanical strength, good hydrophilicity (often achieved through plasma treatment), and solvent resistance; some processes also require low-temperature heat treatment to enhance film stability.
[0003] Currently, the aforementioned technical approach has a significant limitation: it is difficult to directly apply it to water-soluble luminescent organic gel substrates. The reasons are twofold. First, the aqueous solvents used in spin-coating dissolve the gel substrate; and the gas / liquid interface transfer method requires contact with the liquid surface, which can easily cause the gel to swell or structurally damage. Second, the microsphere self-assembly process requires a hydrophilic environment (such as an aqueous or alcoholic phase system), which inherently conflicts with the water sensitivity of the gel material. Conventional hydrophilic surface pretreatments (such as plasma treatment) can even exacerbate gel dissolution. Therefore, existing processes fail to effectively protect water-soluble soft substrates and also fail to overcome the inherent incompatibility between "aqueous self-assembly media" and "water-sensitive luminescent substrates," resulting in the inability to stably construct monolayer photonic crystal structures on functional gel surfaces. Summary of the Invention
[0004] The purpose of this invention is to provide a luminescent organic gel with a surface-modified monolayer silica photonic crystal and its preparation method. The preparation method of this invention realizes the self-assembly of silica microspheres under completely non-aqueous conditions, fundamentally avoiding the problem of dissolution or swelling of the luminescent gel due to contact with aqueous solvents.
[0005] In order to achieve the above-mentioned objectives of the present invention, the following technical solution is adopted:
[0006] The first aspect of this invention provides a method for preparing a luminescent organic gel with a surface-modified monolayer silica photonic crystal, the method comprising the following steps:
[0007] (a) Forming a monolayer of silicon dioxide photonic crystal on the surface of a PDMS substrate;
[0008] (b) The precursor solution is coated on the surface of a PDMS substrate with a monolayer of silica photonic crystal and then photocured. The precursor solution is composed of isopentyltriphenylphosphine bromide, manganese bromide, 1-vinyl-2-pyrrolidone and 1-hydroxycyclohexylphenyl ketone.
[0009] (c) After photocuring is complete, the PDMS substrate is peeled off to obtain the luminescent organic gel of the surface-modified monolayer silica photonic crystal.
[0010] Preferably, forming a monolayer silicon dioxide photonic crystal on the surface of the PDMS substrate includes:
[0011] Monodisperse silica microspheres are dispersed on the surface of a PDMS substrate. Then, another PDMS substrate is used to cover the surface of the monodisperse silica microspheres. Through relative translational friction of the PDMS substrate, the monodisperse silica microspheres form a single-layer structure. After removing the upper PDMS substrate, residual particles on the surface are blown off by airflow.
[0012] Preferably, forming a monolayer silicon dioxide photonic crystal on the surface of the PDMS substrate includes:
[0013] A monolayer silica photonic crystal was prepared by self-assembly on a rigid substrate. Using a PDMS substrate as a transfer template, PDMS was imprinted onto the rigid substrate surface, thereby transferring the monolayer silica photonic crystal onto the PDMS substrate surface.
[0014] Preferably, the mass ratio of isopentyltriphenylphosphine bromide, manganese bromide, 1-vinyl-2-pyrrolidone and 1-hydroxycyclohexylphenyl ketone is (80~85):(20~25):(65~75):(1~2).
[0015] Preferably, the precursor solution is prepared by the following method:
[0016] First, isopentyltriphenylphosphine bromide and manganese bromide are dissolved in 1-vinyl-2-pyrrolidone, then 1-hydroxycyclohexylphenyl ketone is added, and after complete dissolution, ultrasonic treatment is performed.
[0017] Preferably, the coating thickness of the precursor solution is 0.5~2 mm.
[0018] Preferably, the photocuring includes irradiation under 365nm ultraviolet light for 2.5~5 minutes.
[0019] A second aspect of the present invention provides a luminescent organic gel of a surface-modified monolayer silica photonic crystal prepared by the above-described preparation method.
[0020] Compared with the prior art, the beneficial effects of the present invention include at least the following:
[0021] The preparation method of this invention realizes the self-assembly of silica microspheres under completely non-aqueous conditions, fundamentally avoiding the problem of dissolution or swelling of luminescent gels due to contact with aqueous solvents. Specifically, by constructing a monolayer photonic crystal on a rubber temporary substrate, then coating it with a precursor solution of uniform thickness, and after photocuring to form a gel, peeling off the rubber substrate, a structurally complete monolayer photonic crystal can be obtained on the gel surface. This method is completely water-free and applicable to various photocurable water-soluble luminescent gel systems. It effectively overcomes the problem of disordered microsphere arrangement or easy detachment on low surface energy materials, and realizes the controllable preparation of large-area, high-strength monolayer photonic crystals on the surface of luminescent organic gels.
[0022] In addition, this invention achieves functional preservation of water-sensitive substrates by combining low-temperature (<60℃) dry transfer with photocuring interface anchoring technology; this process does not require high-temperature treatment or strong chemical corrosion steps, ensuring complete coverage and good adhesion of the photonic crystal structure in the luminescent active region.
[0023] This invention is the first to successfully integrate a high-quality photonic crystal structure on the surface of an organic gel light-emitting device. By precisely matching the bandgap position with the emission peak of the scintillator, a light output enhancement of more than 60% is achieved, which significantly improves the signal-to-noise ratio and detection sensitivity of the device.
[0024] The preparation method of the present invention prepares a sacrificial layer with a predetermined shape and precise area on a carrier substrate through a predetermined coating process; the coating area of the sacrificial layer strictly defines the physical boundary of the subsequent self-assembly of the photonic crystal, and thus determines the maximum theoretical area of the monolayer photonic crystal luminescent organic gel that can be obtained. Attached Figure Description
[0025] To more clearly illustrate the specific embodiments of the present invention or the technical solutions in the prior art, the accompanying drawings used in the description of the specific embodiments or the prior art will be briefly introduced below. In all the drawings, similar elements or parts are generally identified by similar reference numerals. In the drawings, the elements or parts are not necessarily drawn to scale.
[0026] Figure 1 is a process diagram of the preparation of the luminescent organic gel with surface-modified monolayer silica photonic crystal in Example 1 of the present invention;
[0027] Figure 2 is a SEM image of the luminescent organic gel with surface-modified monolayer silica photonic crystal in the experimental example of the present invention;
[0028] Figure 3 shows the luminescent organic gel of the surface-modified monolayer silica photonic crystal and the X-ray irradiation spectrum of the organic gel in the experimental example of the present invention.
[0029] Figure 4 shows the transparency of the luminescent organic gel without surface-modified monolayer silica photonic crystal in the experimental example of the present invention.
[0030] Figure 5 is an observation of the transparency of the luminescent organic gel of the surface-modified monolayer silica photonic crystal in the experimental example of the present invention;
[0031] Figure 6 shows the luminescent organic gel with surface-modified monolayer silica photonic crystal in the experimental example of the present invention under sunlight. Detailed Implementation
[0032] The embodiments of the technical solution of the present invention will be described in detail below with reference to the examples. The following embodiments are only used to illustrate the technical solution of the present invention more clearly, and are therefore only examples, and should not be used to limit the scope of protection of the present invention.
[0033] It should be noted that, unless otherwise stated, the technical or scientific terms used in this application should have the ordinary meaning as understood by one of ordinary skill in the art to which this invention pertains.
[0034] This invention provides a method for preparing a luminescent organic gel with a surface-modified monolayer silica photonic crystal, the method comprising the following steps:
[0035] (a) Forming a monolayer of silicon dioxide photonic crystal on the surface of a PDMS substrate;
[0036] (b) The precursor solution is coated on the surface of a PDMS substrate with a monolayer of silica photonic crystal and then photocured. The precursor solution is composed of isopentyltriphenylphosphine bromide, manganese bromide, 1-vinyl-2-pyrrolidone and 1-hydroxycyclohexylphenyl ketone.
[0037] (c) After photocuring is complete, the PDMS substrate is peeled off to obtain the luminescent organic gel of the surface-modified monolayer silica photonic crystal.
[0038] In one embodiment, forming a monolayer silicon dioxide photonic crystal on the surface of a PDMS substrate includes:
[0039] Monodisperse silica microspheres are dispersed on the surface of a PDMS substrate. Then, another PDMS substrate is used to cover the surface of the monodisperse silica microspheres. Through relative translational friction of the PDMS substrate, the monodisperse silica microspheres form a single-layer structure. After removing the upper PDMS substrate, residual particles on the surface are blown off by airflow.
[0040] In one embodiment, forming a monolayer silicon dioxide photonic crystal on the surface of a PDMS substrate includes:
[0041] A monolayer silica photonic crystal was prepared by self-assembly on a rigid substrate. Using a PDMS substrate as a transfer template, PDMS was imprinted onto the rigid substrate surface, thereby transferring the monolayer silica photonic crystal onto the PDMS substrate surface.
[0042] In one embodiment, the mass ratio of isopentyltriphenylphosphine bromide, manganese bromide, 1-vinyl-2-pyrrolidone and 1-hydroxycyclohexylphenyl ketone is (80~85):(20~25):(65~75):(1~2).
[0043] In one embodiment, the precursor solution is prepared by the following method:
[0044] First, isopentyltriphenylphosphine bromide and manganese bromide are dissolved in 1-vinyl-2-pyrrolidone, then 1-hydroxycyclohexylphenyl ketone is added, and after complete dissolution, ultrasonic treatment is performed.
[0045] In one embodiment, the coating thickness of the precursor solution is 0.5~2 mm.
[0046] In one embodiment, the photocuring includes irradiation under 365nm ultraviolet light for 2.5 to 5 minutes.
[0047] Another embodiment of the present invention provides a luminescent organic gel of a surface-modified monolayer silica photonic crystal prepared by the above preparation method.
[0048] The technical solution of the present invention will be further described in detail below through specific embodiments.
[0049] Example 1
[0050] This embodiment describes a method for preparing a luminescent organic gel with a surface-modified monolayer silica photonic crystal, as shown in Figure 1. The preparation method includes the following steps:
[0051] (a) The PDMS prepolymer and crosslinking agent were mixed at a mass ratio of 10:1, stirred evenly, and then poured into a polystyrene petri dish, controlling the thickness of the liquid layer to be uniform (about 5 mm); then cured at 60°C for 12 h to obtain the PDMS substrate;
[0052] 500 nm monodisperse silica microspheres were uniformly spread on the surface of a PDMS substrate. Another PDMS substrate was placed on top, and the microspheres were gently pressed and rubbed in relative translation to allow them to self-assemble into a single-layer structure. After removing the upper substrate, residual particles on the surface were blown away with a low-pressure airflow.
[0053] (b) Isopentyltriphenylphosphine bromide (2 mmol, 826.7 mg) and manganese bromide (1 mmol, 214.8 mg) were added to 694.3 mg of 1-vinyl-2-pyrrolidone and stirred until completely dissolved; then 14 mg of 1-hydroxycyclohexylphenyl ketone was added as a photoinitiator, and after being fully dissolved, the mixture was sonicated for 5 min to remove bubbles to obtain a precursor solution. The precursor solution was coated on the surface of a PDMS substrate with a monolayer of silica photonic crystal, and the coating thickness was controlled to be 1 mm. Then, the substrate was irradiated under 365 nm ultraviolet light for 3 min to initiate photopolymerization crosslinking.
[0054] (c) After photocuring is complete, the PDMS substrate is peeled off to obtain the luminescent organic gel of the surface-modified monolayer silica photonic crystal.
[0055] Example 2
[0056] This embodiment describes a method for preparing a luminescent organic gel with a surface-modified monolayer silica photonic crystal. The preparation method includes the following steps:
[0057] (a) The PDMS prepolymer and crosslinking agent were mixed at a mass ratio of 10:1, stirred evenly, and then poured into a polystyrene petri dish, controlling the thickness of the liquid layer to be uniform (about 5 mm); then cured at 60°C for 12 h to obtain the PDMS substrate;
[0058] Monolayer microspheres were prepared by self-assembly on a rigid substrate (silicon wafer), and then PDMS substrate was used as a transfer template to imprint them onto the surface of the rigid substrate, so that the monolayer silicon dioxide photonic crystal was transferred to the surface of the PDMS substrate.
[0059] (b) Isopentyltriphenylphosphine bromide (2 mmol, 826.7 mg) and manganese bromide (1 mmol, 214.8 mg) were added to 694.3 mg of 1-vinyl-2-pyrrolidone and stirred until completely dissolved; then 14 mg of 1-hydroxycyclohexylphenyl ketone was added as a photoinitiator, and after being fully dissolved, the mixture was sonicated for 5 min to remove bubbles to obtain a precursor solution. The precursor solution was coated on the surface of a PDMS substrate with a monolayer of silica photonic crystal, and the coating thickness was controlled to be 1 mm. Then, the substrate was irradiated under 365 nm ultraviolet light for 3 min to initiate photopolymerization crosslinking.
[0060] (c) After photocuring is complete, the PDMS substrate is peeled off to obtain the luminescent organic gel of the surface-modified monolayer silica photonic crystal.
[0061] Compare with Example 1
[0062] This comparative example illustrates a method for preparing an organic gel, which includes the following steps:
[0063] (a) Isopentyltriphenylphosphine bromide (2 mmol, 826.7 mg) and manganese bromide (1 mmol, 214.8 mg) were added to 694.3 mg of 1-vinyl-2-pyrrolidone and stirred until completely dissolved; then 14 mg of 1-hydroxycyclohexylphenyl ketone was added as a photoinitiator, and after complete dissolution, the mixture was sonicated for 5 min to remove bubbles to obtain a precursor solution. The precursor solution was poured into a mold, with a thickness of 1 mm, and then irradiated under 365 nm ultraviolet light for 3 min to initiate photopolymerization crosslinking.
[0064] (b) After the photocuring is complete, remove it from the mold to obtain the organic gel.
[0065] Experimental Example
[0066] Obtain the luminescent organic gel of the surface-modified monolayer silica photonic crystal prepared in Example 1; obtain the organic gel in Comparative Example 1;
[0067] The SEM images of the luminescent organic gel with surface-modified monolayer silica photonic crystal are shown in Figure 2. In Figure 2, the left image is the surface SEM image of the luminescent organic gel with surface-modified monolayer silica photonic crystal, and the right image is the cross-sectional SEM image of the luminescent organic gel with surface-modified monolayer silica photonic crystal.
[0068] As shown in Figure 2, a monolayer of silica photonic crystal is modified on the surface of the luminescent organic gel.
[0069] X-ray spectroscopy was performed on the luminescent organic gel of surface-modified monolayer silica photonic crystal in Example 1 and the organic gel of Control Example 1. The results are shown in Figure 3.
[0070] As shown in Figure 3, under X-ray irradiation excitation, the light-emitting organic gel with a surface-modified monolayer silica photonic crystal of the same thickness has a light yield that is 62.6% higher than that of the organic gel in Control Example 1, indicating that the surface monolayer silica photonic crystal does indeed enhance the light output efficiency of the light-emitting organic gel.
[0071] The luminescent organic gel of the surface-modified monolayer silica photonic crystal of Example 1 and the organic gel of Control Example 1 were observed, and the observation results are shown in Figures 4-5; the luminescent organic gel of the surface-modified monolayer silica photonic crystal of Example 1 was observed under sunlight, and the results are shown in Figure 6.
[0072] As shown in Figures 4-6, the transparency of the luminescent organic gel with surface-modified monolayer silica photonic crystal is not significantly reduced compared to the luminescent organic gel without surface-modified monolayer silica photonic crystal. Moreover, under natural light, the monolayer photonic crystal exhibits a rainbow-colored visual effect that changes with the viewing angle due to the selective diffraction and interference of photons of different wavelengths in the visible light band based on its periodic structure.
[0073] Finally, it should be noted that the above embodiments are only used to illustrate the technical solutions of the present invention, and not to limit them. Although the present invention has been described in detail with reference to the foregoing embodiments, those skilled in the art should understand that modifications can still be made to the technical solutions described in the foregoing embodiments, or equivalent substitutions can be made to some or all of the technical features therein. Such modifications or substitutions do not cause the essence of the corresponding technical solutions to deviate from the scope of the technical solutions of the embodiments of the present invention, and they should all be covered within the scope of the claims and specification of the present invention.
Claims
1. A method for preparing a luminescent organic gel with a surface-modified monolayer silica photonic crystal, characterized in that, The preparation method includes the following steps: (a) forming a monolayer silica photonic crystal on the surface of a PDMS substrate; (b) coating a precursor solution onto the surface of the PDMS substrate with the monolayer silica photonic crystal, and then photocuring it, wherein the precursor solution is composed of isopentyltriphenylphosphine bromide, manganese bromide, 1-vinyl-2-pyrrolidone and 1-hydroxycyclohexylphenyl ketone; (c) after photocuring, peeling off the PDMS substrate to obtain the luminescent organic gel with the surface-modified monolayer silica photonic crystal.
2. The preparation method according to claim 1, characterized in that, The process of forming a monolayer silica photonic crystal on the PDMS substrate surface includes: dispersing monodisperse silica microspheres on the PDMS substrate surface, then covering the surface of the monodisperse silica microspheres with another PDMS substrate and forming a monolayer structure of the monodisperse silica microspheres through relative translational friction of the PDMS substrates, and removing the upper PDMS substrate and then blowing away residual particles on the surface with airflow.
3. The preparation method according to claim 1, characterized in that, The process of forming a monolayer silicon dioxide photonic crystal on the surface of a PDMS substrate includes: preparing a monolayer silicon dioxide photonic crystal on the surface of a rigid substrate by self-assembly; using the PDMS substrate as a transfer template, imprinting PDMS onto the surface of the rigid substrate, thereby transferring the monolayer silicon dioxide photonic crystal onto the surface of the PDMS substrate.
4. The preparation method according to claim 1, characterized in that, The mass ratio of isopentyltriphenylphosphine bromide, manganese bromide, 1-vinyl-2-pyrrolidone and 1-hydroxycyclohexylphenyl ketone is (80~85):(20~25):(65~75):(1~2).
5. The preparation method according to claim 1, characterized in that, The precursor solution was prepared by dissolving isopentyltriphenylphosphine bromide and manganese bromide in 1-vinyl-2-pyrrolidone, then adding 1-hydroxycyclohexylphenyl ketone, and sonicating after complete dissolution.
6. The preparation method according to claim 1, characterized in that, The coating thickness of the precursor solution is 0.5~2mm.
7. The preparation method according to claim 1, characterized in that, The photocuring process involves irradiation under 365nm ultraviolet light for 2.5 to 5 minutes.
8. The luminescent organic gel of a surface-modified monolayer silica photonic crystal prepared by the preparation method according to any one of claims 1 to 7.