Flexible light-emitting film and preparation method and application thereof
By combining PDMS matrix with (ECMP)2MnBr4 crystal, a flexible light-emitting film with stable light-emitting performance under mechanical stress was prepared, which solved the problem of low response efficiency of existing stress-emitting films and can be applied to health monitoring and disaster early warning.
Patent Information
- Application Number
- CN202510890373.9
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2025-06-30
- Publication Date
- 2025-11-07
Smart Images
Figure CN120904684A_ABST
Abstract
Description
TECHNICAL FIELD
[0001] The present application relates to the technical field of light-emitting materials, in particular to a flexible light-emitting film and a preparation method and application thereof. BACKGROUND
[0002] The current stress luminescent film has a large luminescent response threshold after experiencing mechanical stimulation, resulting in an insensitive response. In addition, after the stress luminescent material is mixed and packaged with a colloid, the optical performance of stress luminescence is seriously degraded. SUMMARY
[0003] In view of the technical problems in the background art, the present application provides a flexible light-emitting film and a preparation method and application thereof, aiming to solve the problems of low response efficiency of the existing light-emitting film and degradation of optical performance after mixed and packaged with a colloid.
[0004] In a first aspect, the present application provides a flexible light-emitting film, comprising a PDMS matrix and (ECMP)2MnBr4 crystals dispersed in the PDMS matrix; having a mechanoluminescence performance, within a stretching range of 20-100%, the intensity of the mechanoluminescence performance linearly increases with the tensile strain.
[0005] In the technical scheme of the present application, the light-emitting film uses PDMS as the substrate and transparent (ECMP)2MnBr4 crystals as the light-emitting material, and has good flexibility and visibility. The (ECMP)2MnBr4 crystals trigger mechanoluminescence by hydrogen bond rupture and defect-assisted charge transfer under mechanical stress, so that the stress luminescence performance of the light-emitting film is stable and recoverable. Within a stretching range of 20-100%, the ML intensity linearly increases with the tensile strain, and the luminescence performance is sensitive.
[0006] In a second aspect, the present application provides an application of the flexible light-emitting film, which is applied to the fields of health monitoring, disaster warning of landslides and crack expansion.
[0007] In a third aspect, the present application provides a preparation method of the flexible light-emitting film, comprising the following preparation steps:
[0008] S1. Adding ethoxycarbonylmethyl (triphenyl) phosphonium bromide and manganese bromide powder into anhydrous ethanol, heating and stirring until completely dissolved to obtain a mixed solution;
[0009] S2. Cooling the mixed solution and stopping stirring to precipitate crystals;
[0010] S3. Drying the crystals to obtain (ECMP)2MnBr4 crystals;
[0011] S4. Disperse the (ECMP)2MnBr4 crystals in PDMS, and dry to obtain a (ECMP)2MnBr4@PDMS film.
[0012] In the technical scheme of the embodiment, ethoxycarbonylmethyl (triphenyl) phosphonium bromide and MnBr4 are dissolved in an ethanol solvent to crystallize at a low temperature by a solution crystallization method to obtain transparent (ECMP)2MnBr4 crystals. The crystals have sensitive and repeatable luminescence performance, and a flexible stress-responsive luminescent film is obtained by mixing the crystals with PDMS.
[0013] In some embodiments, in step S4, the mass ratio of the (ECMP)2MnBr4 crystals to PDMS is 1:1-3.
[0014] In the embodiment, by mixing the luminescent material crystals and the PDMS substrate in a specific ratio, the flexible luminescent material maintains good luminescence performance while having good mechanical properties.
[0015] In some embodiments, in step S4, the drying temperature is 50-80℃.
[0016] In the embodiment, by drying at a specific temperature, the mechanical properties of the flexible material are maintained well.
[0017] In some embodiments, in step S1, the molar ratio of ethoxycarbonylmethyl (triphenyl) phosphonium bromide to manganese bromide is 2:1; the concentration of ethoxycarbonylmethyl (triphenyl) phosphonium bromide in the mixed solution is 17-19% (w / v), and the concentration of manganese bromide is 4-5% (w / v).
[0018] In the embodiment, ethoxycarbonylmethyl (triphenyl) phosphonium bromide and manganese bromide are dissolved in ethanol in a specific concentration and ratio, and the coordination assembly of ECMPBr and MnBr2 is more sufficient.
[0019] In some embodiments, in step S1, the heating temperature is 80-150℃; the stirring speed is 300-500 r / min, and the stirring time is 30-90 min.
[0020] In the embodiment, by heating, ECMPBr and MnBr2 are fully dissolved in anhydrous ethanol. If the temperature is too high, the solvent is easily volatilized and lost. If the temperature is too low, the ECMPBr and MnBr2 powder cannot be dissolved in the solvent. By stirring, the mixture is dissolved faster and the reaction is more sufficient.
[0021] In some embodiments, in step S2, the cooling temperature is 25-80℃.
[0022] In this embodiment, the synthesized (ECMP)2MnBr4crystals can be stably precipitated by cooling at a suitable temperature. If the temperature is too high, the solvent will quickly evaporate and the crystals cannot be precipitated. If the temperature is too low, the crystals cannot be uniformly precipitated or cannot be precipitated.
[0023] In some embodiments, the temperature for drying in step S3 is 50-70°C.
[0024] In this embodiment, the (ECMP)2MnBr4crystals are dried by baking.
[0025] The above description is only a summary of the technical solutions of the present application. In order to more clearly understand the technical means of the present application, the following specific embodiments of the present application can be implemented according to the content of the description, and in order to make the above and other purposes, features and advantages of the present application more obvious and easy to understand, the following specific embodiments of the present application are described. BRIEF DESCRIPTION OF DRAWINGS
[0026] In order to more clearly illustrate the technical solutions of the present application, the following will briefly introduce the drawings used in the present application. Obviously, the drawings described below are only some embodiments of the present application, and those skilled in the art can obtain other drawings according to these drawings without creating any creative labor.
[0027] Figure 1 The photos of (ECMP)2MnBr4@PDMS film prepared in Example 1 under different mechanical stimuli (friction, extrusion and stretching).
[0028] Figure 2 The ML performance diagram of (ECMP)2MnBr4@PDMS film prepared in Example 1.
[0029] Figure 3 The luminescence effect principle diagram of luminescent material (ECMP)2MnBr4crystals in (ECMP)2MnBr4@PDMS film prepared in Example 1 under different mechanical stimuli (friction, extrusion and stretching).
[0030] Figure 4 The stretching-luminescence intensity diagram of (ECMP)2MnBr4@PDMS film prepared in Example 1.
[0031] Figure 5 The stress luminescence and comparison before and after stretching of (ECMP)2MnBr2@PDMS film prepared in Examples 2-3 and Comparative Examples 1-2.
[0032] Figure 6 The morphology comparison diagram of (ECMP)2MnBr2@PDMS film prepared in Examples 4-5 and Comparative Examples 3-4.
[0033] Figure 7 Stress response and simulated disaster warning map of the (ECMP)2MnBr4@PDMS film prepared in Example 1. DETAILED DESCRIPTION
[0034] The embodiments of the technical solutions of the present application are described in detail below. The following examples are only used to more clearly illustrate the technical solutions of the present application, and therefore only serve as examples, and cannot limit the protection scope of the present application.
[0035] Unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this application belongs; the terms "comprising" and "having", and any variations thereof, used herein are only for the purpose of describing the specific embodiments of the present application, and are not intended to limit the present application.
[0036] Reference herein to "an embodiment" means that a particular feature, structure, or characteristic described in connection with the embodiment can be included in at least one embodiment of the application. The appearance of the phrase in various places in the specification does not necessarily all refer to the same embodiment, nor is it necessarily mutually exclusive of other embodiments. It will be explicitly understood by one of ordinary skill in the art that the embodiments described herein can be combined with other embodiments.
[0037] In order to solve the problem that the existing light-emitting film has low response efficiency and is difficult to reuse, the present application provides a flexible light-emitting film and a preparation method and application thereof. The light-emitting film of the present application has a PDMS as a substrate and a transparent (ECMP)2MnBr4 crystal as a light-emitting material, and has good flexibility and visibility. The (ECMP)2MnBr4 crystal triggers mechanoluminescence by hydrogen bond rupture and defect-assisted charge transfer under mechanical stress, so that the stress luminescence performance of the light-emitting film is stable and recoverable. In a stretching range of 20-100%, the intensity of mechanical luminescence (ML) increases linearly with the tensile strain, and the luminescence performance is sensitive. The flexible light-emitting film prepared by the present application has a green and simple preparation process, and the raw materials are non-toxic and harmless. The flexible light-emitting material has fast and high-sensitivity fluorescence response to mechanical stimulation, and has good application prospect in the field of disaster warning (landslide, crack propagation).
[0038] In one aspect, the present application provides a flexible light-emitting film, comprising a PDMS matrix and (ECMP)2MnBr4 crystals dispersed in the PDMS matrix; having mechanical luminescence performance, and in a stretching range of 20-100%, the intensity of the mechanical luminescence performance increases linearly with the tensile strain.
[0039] The technical scheme of the embodiment of the present application has the following advantages: the luminescent film has PDMS as a substrate and has (ECMP)2MnBr4 crystals as luminescent materials, and has good flexibility and visibility. The (ECMP)2MnBr4 crystals trigger mechanoluminescence through hydrogen bond rupture and defect-assisted charge transfer under mechanical stress, so that the stress luminescence performance of the luminescent film is stable and recoverable. In a tensile range of 20-100%, the ML intensity linearly increases with tensile strain, and the luminescence performance is sensitive.
[0040] In a second aspect, the present application provides a flexible luminescent film and application thereof. The flexible luminescent film is applied to the field of disaster warning of landslides and crack propagation.
[0041] In a third aspect, the present application provides a preparation method of a flexible luminescent film. The preparation method comprises the following steps:
[0042] S1. Adding ethoxycarbonylmethyl (triphenyl) phosphonium bromide and manganese bromide powder into anhydrous ethanol, and heating and stirring until completely dissolved to obtain a mixed solution;
[0043] S2. Cooling the mixed solution and stopping stirring to precipitate crystals;
[0044] S3. Drying the crystals to obtain (ECMP)2MnBr4 crystals;
[0045] S4. Dispersing the (ECMP)2MnBr4 crystals in PDMS, and drying to obtain (ECMP)2MnBr4@PDMS film.
[0046] In the technical scheme of the embodiment of the present application, ethoxycarbonylmethyl (triphenyl) phosphonium bromide and MnBr4 are dissolved in ethanol solvent to crystallize at low temperature by a solution crystallization method, and transparent (ECMP)2MnBr4 crystals are obtained. The crystals have sensitive and repeatable luminescence performance, and the flexible stress response luminescent film is obtained by mixing the crystals with PDMS.
[0047] Further, in some embodiments, in step S4, the mass ratio of the (ECMP)2MnBr4 crystals to PDMS is 1:1-3.
[0048] In the technical scheme of the embodiment of the present application, by mixing the luminescent material crystals and the PDMS substrate in a specific ratio, the flexible luminescent material has good luminescence performance and good mechanical properties.
[0049] Further, in some embodiments, in step S4, the drying temperature is 50-80°C.
[0050] In the technical scheme of the embodiment of the present application, by drying at a specific temperature, the mechanical properties of the flexible material are maintained.
[0051] Further, in some embodiments, in step S1, the molar ratio of the ethoxycarbonylmethyl (triphenyl) phosphonium bromide and manganese bromide is 2:1; the concentration of the ethoxycarbonylmethyl (triphenyl) phosphonium bromide in the mixed solution is 17-19% (w / v), and the concentration of the manganese bromide is 4-5% (w / v).
[0052] In the technical scheme of the embodiments of the present application, the ethoxycarbonylmethyl (triphenyl) phosphonium bromide and manganese bromide of specific concentration and ratio are dissolved in ethanol, and the coordination assembly of ECMPBr and MnBr2 is more sufficient.
[0053] Further, in some embodiments, in step S1, the heating temperature is 80-150℃; the stirring speed is 300-500 r / min, and the stirring time is 30-90 min.
[0054] In the technical scheme of the embodiments of the present application, the ECMPBr and MnBr2 are fully dissolved in anhydrous ethanol by heating, the solvent is easily lost by volatilization at too high temperature, and the ECMPBr and MnBr2 powder cannot be dissolved in the solvent at too low temperature, the mixture is dissolved faster by stirring, and the reaction is more sufficient.
[0055] Further, in some embodiments, in step S2, the cooling temperature is 25-80℃.
[0056] In the technical scheme of the embodiments of the present application, the synthesized (ECMP)2MnBr4 crystals can be stably precipitated by cooling at a suitable temperature, the crystals cannot be precipitated at too high temperature because the solvent volatilizes quickly, and the crystals cannot be uniformly precipitated or cannot be precipitated at too low temperature.
[0057] Further, in some embodiments, in step S3, the drying temperature is 50-70℃.
[0058] In the technical scheme of the embodiments of the present application, the (ECMP)2MnBr4 crystals are obtained by drying.
[0059] Some specific embodiments are listed below, and it should be noted that the embodiments described below are exemplary and are used to explain the present application, and cannot be understood as a limitation on the present application. If the specific technology or condition is not specified in the embodiments, the technology or condition described in the literature in the art or according to the product manual is used. If the reagent or instrument is not specified by the manufacturer, it is a conventional product that can be obtained by purchase.
[0060] Embodiment 1
[0061] The embodiment provides a preparation method of a flexible light-emitting film, and specifically includes the following steps:
[0062] (1) Weigh 2 mmol of ECMPBr and 1 mmol of MnBr2 and add them to 5 mL of anhydrous ethanol. Stir at 400 r / min for 1 h on a heating plate at 100 °C to obtain a mixed solution.
[0063] (2) Cool the mixed solution to 70°C and stop stirring to precipitate crystals.
[0064] (3) The precipitated crystals were dried at 60°C to obtain (ECMP)2MnBr4 crystals.
[0065] (4) After grinding (ECMP)2MnBr4 crystals at a mass ratio of 1:2, mix them with PDMS in a petri dish, pour the mixture into a mold, and dry it in an oven at 60°C to obtain (ECMP)2MnBr4@PDMS film.
[0066] Figure 1 These are photographs of the (ECMP)2MnBr4@PDMS film prepared in this embodiment under friction, extrusion, and stretching conditions.
[0067] Depend on Figure 1 As can be seen, the (ECMP)2MnBr4@PDMS film prepared in this embodiment emits obvious green fluorescence under mechanical stimulation (friction, extrusion and stretching).
[0068] The ML properties of the (ECMP)2MnBr4@PDMS thin film prepared in this embodiment were tested, and the results are as follows: Figure 2 As shown.
[0069] Depend on Figure 2 It can be seen that the mechanoluminescence and photoluminescence spectra of the luminescent material (ECMP)2MnBr4 crystal in the (ECMP)2MnBr4@PDMS thin film prepared in this embodiment are basically consistent, both originating from Mn 2+ The dd transition emits light.
[0070] Figure 3 This is a schematic diagram illustrating the luminescence effect of the (ECMP)2MnBr4 crystal in the (ECMP)2MnBr4@PDMS film prepared in this embodiment under different mechanical stimuli (friction, extrusion, and stretching).
[0071] Depend on Figure 3 It can be seen that the (ECMP)2MnBr4@PDMS thin film prepared in this embodiment can achieve efficient energy transfer and carrier recombination under different mechanical stimuli (friction, extrusion and stretching), thereby exciting typical Mn 2+ 6A1→ 4T1 green light. Specifically, the rubbing action produces a large number of free electrons and holes through surface charge separation, and promotes the release of trapped carriers in shallow traps and deep traps in turn; in the process of extrusion, the local stress concentration forms a new trap release path, which injects more carriers into the conduction band and accelerates the recombination luminescence; and the tensile deformation fine-tunes the energy level structure by changing the lattice strain and trap distribution, thereby optimizing the energy transfer efficiency from the trap to the Mn 2+ energy transfer efficiency of the luminescent center.
[0072] The quantitative evaluation of the (ECMP)2MnBr4@PDMS film prepared in this embodiment was carried out by using an optical and mechanical test system, and the results are shown in Figure 4 .
[0073] As can be seen from Figure 4 , the ML intensity of the (ECMP)2MnBr4@PDMS film prepared in this embodiment increases linearly with the tensile strain in the tensile range of 20-100%.
[0074] Examples 2-3 and Comparative Examples 1-2
[0075] Examples 2-3 and Comparative Examples 1-2 respectively provide a preparation method of a flexible luminescent film, which differs from Example 1 in that the ratio of (ECMP)2MnBr4 crystals and PDMS in step (4) is different, as shown in Table 1, and the other steps are substantially the same as those of Example 1, which will not be repeated here.
[0076] Table 1 Mass ratio of (ECMP)2MnBr4 crystals and PDMS in Examples 2-3 and Comparative Examples 1-2
[0077]
[0078] The (ECMP)2MnBr4@PDMS film prepared in Examples 2-3 and Comparative Examples 1-2 was respectively subjected to tensile test, and the results are shown in Figure 5 .
[0079] As can be seen from the results in Figure 5 , Examples 2 and 3 can emit bright green fluorescence under stress; Comparative Example 2 emits weak light under stress; the film prepared in Comparative Example 1 has very low tensile strength, necks and rapidly breaks at a very small strain, with an elongation at break of less than 10%, showing obvious brittle fracture characteristics.
[0080] Examples 4-5 and Comparative Examples 3-4
[0081] Examples 4-5 and Comparative Examples 3-4 provide a method for preparing a flexible light-emitting film. The difference between Example 1 and Example 2 is that the drying temperature in step (4) is different, as shown in Table 2. The other steps are roughly the same as in Example 1 and will not be repeated here.
[0082] Table 2 shows the drying temperatures in Examples 4-5 and Comparative Examples 3-4.
[0083] Case Example 4 Example 5 Comparative Example 3 Comparative Example 4 Drying temperature (°C) 50 80 40 150
[0084] The morphology of the (ECMP)2MnBr4@PDMS films prepared in Examples 4-5 and Comparative Examples 3-4 was evaluated, and the results are as follows: Figure 6 As shown.
[0085] Depend on Figure 6 The results show that the films prepared in Examples 4 and 5 have complete morphology, the film in Comparative Example 3 cannot be formed at the drying temperature, and the internal crystals of the film in Comparative Example 4 begin to melt at the drying temperature, and the film turns yellowish-brown.
[0086] Figure 7 The image shows the stress response and disaster early warning simulation of the (ECMP)2MnBr4@PDMS thin film prepared in Example 1 of this application.
[0087] In summary, this application provides a flexible luminescent film, its preparation method, and its applications. The luminescent film of this application uses PDMS as a substrate and transparent (ECMP)2MnBr4 crystal as the luminescent material, exhibiting good flexibility and visibility. Under mechanical stress, the (ECMP)2MnBr4 crystal triggers mechanoluminescence through hydrogen bond breaking and defect-assisted charge transfer, resulting in stable and recoverable stress-induced luminescence performance of the luminescent film. Within a tensile range of 20–100%, the mechanoluminescence (ML) intensity increases linearly with tensile strain, demonstrating sensitive luminescence performance. The flexible luminescent film prepared by this invention utilizes a green and simple preparation process with non-toxic raw materials. The flexible luminescent material exhibits rapid fluorescence response to mechanical stimuli and high sensitivity, showing promising application prospects in disaster early warning (landslides, crack propagation).
[0088] It should be noted that this application is not limited to the above-described embodiments. The above embodiments are merely examples, and any embodiments with the same structure and effect as the technical concept within the scope of this application are included in the technical scope of this application. Furthermore, various modifications that can be conceived by those skilled in the art to the embodiments, and other ways of constructing by combining some of the constituent elements of the embodiments, without departing from the spirit of this application, are also included in the scope of this application.
Claims
1. A flexible light emitting film, characterized in that, The flexible luminescent film comprises a PDMS matrix and (ECMP)2MnBr4 crystals dispersed in the PDMS matrix.
2. The flexible light emitting film of claim 1, wherein, The mechanical luminescence performance is linearly increased with tensile strain in a tensile range of 20-100%.
3. Use of a flexible light emitting film, characterized in that The flexible luminescent film as claimed in claims 1-2 is applied to the fields of health monitoring and disaster warning of landslides and crack propagation.
4. A method of making a flexible light-emitting film, characterized by, The flexible luminescent film as claimed in claims 1-2 comprises the following preparation steps: S1. adding ethoxycarbonylmethyl (triphenyl) phosphonium bromide and manganese bromide powder into anhydrous ethanol, heating and stirring until completely dissolved to obtain a mixed solution; S2. cooling the mixed solution and stopping stirring to precipitate crystals; S3. drying the crystals to obtain (ECMP)2MnBr4 crystals; S4. uniformly dispersing the (ECMP)2MnBr4 crystals in PDMS, drying to obtain (ECMP)2MnBr4@PDMS flexible film.
5. The method for preparing the flexible light-emitting film according to claim 3, characterized in that, In step S4, the mass ratio of the (ECMP)2MnBr4 crystals to PDMS is 1:1-3.
6. The method for preparing the flexible light-emitting film according to claim 3, characterized in that, In step S4, the drying temperature is 50-80℃.
7. The method for preparing the flexible light-emitting film according to claim 3, characterized in that, In step S1, the molar ratio of ethoxycarbonylmethyl (triphenyl) phosphonium bromide to manganese bromide is 2:1; the concentration of ethoxycarbonylmethyl (triphenyl) phosphonium bromide in the mixed solution is 17-19% (w / v), and the concentration of manganese bromide is 4-5% (w / v).
8. The method for preparing the flexible light-emitting film according to claim 3, characterized in that, In step S1, the heating temperature is 80-150℃; the stirring speed is 300-500 r / min, and the stirring time is 30-90 min.
9. The method for preparing the flexible light-emitting film according to claim 3, characterized in that, In step S2, the cooling temperature is 25-80℃.
10. The method for preparing the flexible light-emitting film according to claim 3, characterized in that, In step S3, the drying temperature is 50-70℃.