Solid-state light emitting material, method for preparing the same, and light emitting method

Abstract

The application relates to a solid light-emitting material and a preparation method and a light-emitting method thereof. The solid light-emitting material comprises a high-molecular polymer which is in a solid film state and can be electrified by contact, and electroluminescent particles which are filled in the high-molecular polymer and at least part of the electroluminescent particles are embedded in the surface of the high-molecular polymer. The electroluminescent particles in the solid light-emitting material provided by the application are firmly combined with the high-molecular polymer and can form a stable structure. The selected high-molecular polymer is easy to be electrified by contact and can generate a strong electric field after being contacted with a liquid drop. Since at least part of the electroluminescent particles are embedded in the surface of the high-molecular polymer, the electroluminescent particles are directly in the electric field formed by the electrification by contact, and the electroluminescent particles are subjected to the action of the strong electric field and continuously emit light with high intensity.

Description

TECHNICAL FIELD

[0001] The present application relates to the technical field of electroluminescence, in particular to a solid-state luminescent material, a preparation method thereof and a luminescent method. BACKGROUND

[0002] The process of liquid flowing on the surface of a solid has been a concern in scientific research, industrial production and life. In scientific research, the interface slip state of the fluid at the solid surface is closely related to the contact form of the liquid at the surface interface. In industrial production and life, the visualization of the liquid flow trajectory has a wide application market in low-quality energy collection, sensing display, etc.

[0003] When the liquid contacts the solid surface, charge transfer occurs, and a certain electric field is generated at the gap between the solid and the liquid. It has been reported that the electric field and electroluminescence can be combined to form a passive self-driven luminescent display device. As described in document 1 (Nano energy. 2020. 104823.) and document 2 (Applied Materials Today. 2021. 101081.), when a liquid droplet hits the surface of a solid device, the contact between the solid and the liquid generates electricity, and a strong electric field is generated on the surface of the device. The electroluminescent material near the surface of the solid device is excited by the electric field and emits light.

[0004] However, in document 1, the device itself adopts a sandwich structure of “electricity-generating film-luminescent particle layer-electricity-generating film layer”. There is no adhesion between the luminescent particle layer and the electricity-generating layer, and the layers are easy to separate, so the device structure is unstable. If a certain amount of adhesive is mixed in the luminescent layer, the excitation effect of the electricity-generating electric field on the luminescent particles will be affected, and the luminescent intensity will be reduced. In addition, the surface electric field generated by the contact between the solid and the liquid in this structure is still a certain distance from the luminescent particles, and the excitation effect of the electric field on the luminescent particles has not reached the maximum utilization efficiency, and the luminescent brightness is relatively low.

[0005] Although the thin film prepared in document 2 is stable in structure, the liquid droplet luminescent display needs to be pre-treated by surface friction contact, and the water droplet can only emit light once after contact, and cannot emit light continuously. The luminescent brightness is also very weak. SUMMARY

[0006] Therefore, the present application provides a solid-state luminescent material with a stable structure and a preparation method thereof. The solid-state luminescent material does not need to be pretreated and can directly produce high-intensity continuous luminescence after the surface contacts with the liquid.

[0007] Further, the present application also provides a luminescent method.

[0008] In a first aspect, the present application provides a solid-state luminescent material, comprising:

[0009] a high-molecular polymer which is in a solid thin film shape and can be electrified; and

[0010] electroluminescent particles which are filled in the high-molecular polymer, and at least part of the electroluminescent particles are embedded in the surface of the high-molecular polymer.

[0011] In some embodiments, the thickness of the solid light-emitting material is 1 to 2 times the diameter of the electroluminescent particles.

[0012] In some embodiments, the mass of the electroluminescent particles accounts for 10% to 40% of the sum of the mass of the high-molecular polymer and the mass of the electroluminescent particles.

[0013] In some embodiments, the high-molecular polymer comprises one or more of polyfluorinated ethylene-propylene, polytetrafluoroethylene, polyvinylidene fluoride, ethylene-tetrafluoroethylene copolymer, polyvinyl chloride, polyethylene, and nylon.

[0014] In some embodiments, the electroluminescent particles comprise one or more of zinc sulfide doped with copper, zinc sulfide doped with manganese, strontium sulfide doped with copper, and strontium sulfide doped with cerium.

[0015] In a second aspect, the present application further provides a preparation method of the solid light-emitting material as described in any one of the embodiments of the first aspect, comprising the following steps:

[0016] providing a high-molecular polymer which can be electrified, making the high-molecular polymer in a solid thin film shape, and filling electroluminescent particles in the high-molecular polymer, and making at least part of the electroluminescent particles embedded in the surface of the high-molecular polymer.

[0017] In some embodiments, the step of making the high-molecular polymer in a solid thin film shape and filling electroluminescent particles in the high-molecular polymer, and making at least part of the electroluminescent particles embedded in the surface of the high-molecular polymer comprises:

[0018] mixing and dispersing a dispersion liquid containing the high-molecular polymer with the electroluminescent particles to prepare a first dispersion liquid;

[0019] coating the first dispersion liquid on a substrate;

[0020] making the dispersant in the first dispersion liquid coated on the substrate volatilize to form a preformed thin film;

[0021] The preformed thin film is heated and solidified to form a solid thin film of the polymer and to fill the electroluminescent particles in the polymer, and at least part of the electroluminescent particles are embedded in the surface of the polymer.

[0022] In some embodiments, the first dispersion is applied to the substrate by spin coating at a speed of 300 rpm to 1100 rpm for 1 minute to 3 minutes.

[0023] In some embodiments, the polymer is formed into a solid thin film and the electroluminescent particles are filled in the polymer, and the step of embedding at least part of the electroluminescent particles in the surface of the polymer comprises:

[0024] The powdered polymer and the electroluminescent particles are dispersed in a dispersant to form a second dispersion;

[0025] The second dispersion is filtered to collect the residue and dry to form a solid mixture of the polymer and the electroluminescent particles;

[0026] The solid mixture is hot-pressed or cold-pressed and then heated and solidified to form a solid thin film of the polymer and to fill the electroluminescent particles in the polymer, and at least part of the electroluminescent particles are embedded in the surface of the polymer.

[0027] In a third aspect, the present application also provides a method for emitting light, comprising the following steps:

[0028] A liquid is contacted with the solid light-emitting material according to any one of the embodiments of the first aspect.

[0029] In the solid light-emitting material provided by the present application, at least part of the electroluminescent particles are embedded in the surface of the polymer by embedding, and the electroluminescent particles are firmly combined with the polymer to form a stable structure. The selected polymer is easy to contact electrification and can be electrified to form a strong electric field after being contacted with a liquid drop. Since at least part of the electroluminescent particles are embedded in the surface of the polymer, the electroluminescent particles are directly in the electric field formed by the electrification, and the electroluminescent particles emit light at high intensity under the action of the strong electric field. The polymer in the solid light-emitting material has good contact electrification performance and can be directly electrified to form a strong electric field without other pre-treatment such as rubbing and accumulating charges, so that the solid light-emitting material can continuously emit light when continuously contacted with a liquid. BRIEF DESCRIPTION OF DRAWINGS

[0030] Figure 1This is a schematic diagram of the preparation process of the solid-state luminescent material in some embodiments of this application;

[0031] Figure 2 The image shows the morphology of the solid luminescent material prepared in Example 1 under an optical microscope (magnification × 100).

[0032] Figure 3 The image shows the morphology of the solid luminescent material prepared in Example 1 under an optical microscope (magnification × 1000).

[0033] Figure 4 SEM scan image of the solid luminescent material prepared in Example 1;

[0034] Figure 5 To Figure 4 SEM scan image after local orientation adjustment;

[0035] Figure 6 To Figure 4 The test spectrum obtained by performing energy dispersive spectroscopy on a local region;

[0036] Figure 7 for Figure 6 Elemental analysis results obtained from energy dispersive spectroscopy (EDS);

[0037] Figure 8 These are physical images of the solid-state luminescent materials prepared in Examples 1 and 2;

[0038] Figure 9 The images show physical images of the solid luminescent materials prepared in Examples 5, 6, 4, and 5.

[0039] Figure 10 The results are the luminescence intensity test results of the solid luminescent materials prepared in Examples 1 and 3.

[0040] Figure 11 The results are the luminescence intensity test results of the solid luminescent materials prepared in Examples 1 and 4;

[0041] Figure 12 This is a comparison of the emission spectra of the solid luminescent materials prepared in Example 1 and Comparative Examples 1 to 3.

[0042] Figure 13 The results are the luminescence intensity test results of the solid luminescent materials prepared in Example 1 and Comparative Examples 1 to 3. Detailed Implementation

[0043] For the purpose of understanding the present application, the present application will be described in further detail by embodiments. The present application may, however, be embodied in many different forms and should not be construed as limited to the embodiments set forth herein. Rather, these embodiments are provided so that this disclosure will be thorough and complete, and fully convey the scope of the application to those skilled in the art.

[0044] 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 terminology used in the description of the application herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the application. The use of the terms "and / or" (and / or) includes a set of one or more associated listed items.

[0045] In the present application, the technical features described in an open-ended manner include both a closed technical solution consisting of listed features and an open technical solution containing listed features.

[0046] In the description of the present application, it should be understood that the terms "center", "longitudinal", "transverse", "length", "width", "thickness", "upper", "lower", "front", "rear", "left", "right", "vertical", "horizontal", "top", "bottom", "inner", "outer", "clockwise", "counterclockwise", "axial", "radial", "circumferential" and the like indicate the orientation or positional relationship based on the orientation or positional relationship shown in the drawings, and are only for the purpose of facilitating the description of the present application and simplifying the description, and do not indicate or imply that the device or element referred to must have a particular orientation, be constructed and operated in a particular orientation, and therefore cannot be understood as limiting the present application.

[0047] The terms "first", "second", "third", "fourth" and the like (if any) used in the present application are used to distinguish similar objects and are only for the purpose of description, and do not necessarily have to describe a particular order or sequence, and cannot be understood as indicating or implying relative importance or implicitly indicating the number of technical features indicated. Therefore, the features defined with "first", "second" can explicitly or implicitly include at least one of the features. In the description of the present application, the meaning of "plurality" is at least two, such as two, three, etc., unless otherwise specifically limited.

[0048] In the present application, unless specifically defined and limited otherwise, the terms "mounting", "connecting", "connecting", "fixing" and the like should be broadly understood, for example, can be fixed connection, can also be detachable connection, or integrated; can be mechanical connection, can also be electrical connection; can be directly connected, can also be indirectly connected through an intermediate medium, can be the internal communication of two elements or the interaction relationship of two elements, unless otherwise specifically limited. For those skilled in the art, the specific meaning of the above terms in the present application can be understood according to the specific circumstances.

[0049] In the present application, the terms "preferably", "more preferably", "more preferably", "preferably" are only used to describe the better effect of the embodiments or examples, and it should be understood that they do not constitute a limitation on the scope of protection of the present application.

[0050] In the present application, the terms "further", "further", "particularly" and the like are used for the purpose of description, indicating the difference in content, but should not be understood as a limitation on the scope of protection of the present application.

[0051] In the present application, "optionally", "optional", "optional" means optional, that is, selected from "yes" or "no" two parallel schemes. If there are multiple "optional" in a technical solution, unless otherwise specified, and there is no contradictory relationship or mutual restriction, each "optional" is independent.

[0052] In the present application, the numerical interval (i.e. the numerical range) is not specifically mentioned, and the optional numerical distribution within the numerical interval is considered to be continuous, and includes the two numerical endpoints (i.e. the minimum value and the maximum value) of the numerical range, and each numerical value between the two numerical endpoints. In addition, when multiple ranges are provided to describe characteristics or characteristics, these ranges can be combined. In other words, unless otherwise specified, the ranges disclosed herein should be understood to include any and all sub-ranges included therein.

[0053] In addition, the drawings are not drawn in a 1:1 ratio, and the relative sizes of the elements are only drawn in the drawings for the purpose of understanding the present application, but not necessarily in true proportion, and the proportions in the drawings do not constitute a limitation on the present application.

[0054] In the first aspect, the present application provides a solid-state light-emitting material, comprising:

[0055] A high molecular polymer, the high molecular polymer is in a solid film state and can be electrified; and

[0056] Electroluminescent particles, the electroluminescent particles are filled in the high molecular polymer, and at least part of the electroluminescent particles are embedded on the surface of the high molecular polymer.

[0057] The solid-state light-emitting material provided in the present application has at least part of the electroluminescent particles embedded on the surface of the polymer polymer by inlaying. The electroluminescent particles are firmly combined with the polymer polymer, and a stable structure can be formed. The selected polymer polymer is easy to contact electrification, and can be electrified to generate a strong electric field after contacting with the liquid droplets. Since at least part of the electroluminescent particles are embedded on the surface of the polymer polymer, the electroluminescent particles are directly in the electric field formed by the contact electrification, and the electroluminescent particles are subjected to the action of the strong electric field to emit high-intensity light. The polymer polymer in the solid-state light-emitting material has good contact electrification performance, and does not need to be pre-treated by rubbing and accumulating charges, but can be directly contacted and electrified to generate a strong electric field, so that the solid-state light-emitting material can continuously emit light in continuous contact with the liquid.

[0058] It can be understood that in the present application, all the electroluminescent particles can be embedded on the surface of the polymer polymer, or part of the electroluminescent particles can be embedded on the surface of the polymer polymer, and the remaining part of the electroluminescent particles can be wrapped inside the polymer polymer. The combination mode of the electroluminescent particles and the polymer polymer is related to the thickness of the solid thin film of the polymer polymer. The smaller the thickness, the higher the proportion of the electroluminescent particles embedded on the surface of the polymer polymer.

[0059] In some embodiments, the thickness of the solid-state light-emitting material is 1 to 2 times the diameter of the electroluminescent particles. The overall thickness of the solid-state light-emitting material is controlled to be close to the size of the diameter of the electroluminescent particles, so that the overall thickness of the solid-state light-emitting material is thin, and the electroluminescent particles are closer to the contact interface of the liquid droplets and the polymer polymer. Therefore, the electroluminescent particles can be closer to the electric field formed by the contact electrification of the solid-liquid, which is more conducive to enhancing the light-emitting intensity.

[0060] It can be understood that under the above conditions, there are about 1 to 2 electroluminescent particles embedded on the surface of the polymer polymer along the thickness direction of the solid-state light-emitting material.

[0061] In some embodiments, the mass of the electroluminescent particles accounts for 10% to 40% of the sum of the mass of the polymer polymer and the mass of the electroluminescent particles. Controlling the mass of the electroluminescent particles and the mass of the polymer polymer within the above proportion range can not only ensure that the liquid can generate a strong electric field after contacting with the polymer polymer, but also ensure that the electroluminescent particles can generate high-intensity light under the action of the electric field. Preferably, the mass of the electroluminescent particles accounts for 25% to 35% of the sum of the mass of the polymer polymer and the mass of the electroluminescent particles.

[0062] In some embodiments, the high molecular polymer includes one or more of fluorinated ethylene propylene (FEP), polytetrafluoroethylene, polyvinylidene fluoride, ethylene-tetrafluoroethylene copolymer, polyvinyl chloride, polyethylene, and nylon. The high molecular polymer has good triboelectric charging effect. Preferably, the high molecular polymer is fluorinated ethylene propylene, which has high fluorine content and strong triboelectric charging performance.

[0063] It is understood that the electroluminescent particles in the present application are any solid luminescent material capable of electroluminescence, which are not particularly limited in the present application and should be understood as within the protection scope of the present application. In some embodiments, the electroluminescent particles include one or more of zinc sulfide doped with copper, zinc sulfide doped with manganese, strontium sulfide doped with copper, and strontium sulfide doped with cerium.

[0064] In a second aspect, the present application further provides a preparation method of the solid luminescent material according to any one of the embodiments of the first aspect, which includes the following steps:

[0065] The high molecular polymer capable of triboelectric charging is provided in a solid thin film form, and the electroluminescent particles are filled on the high molecular polymer, and at least part of the electroluminescent particles are embedded on the surface of the high molecular polymer.

[0066] The solid luminescent material prepared by the preparation method provided by the present application is in a thin film form, has stable structure, and has relatively thin thickness. The electroluminescent particles can be embedded on the surface of the high molecular polymer, close to the contact interface between the high molecular polymer and the liquid, thereby being closer to the electric field formed by triboelectric charging, which is conducive to continuous, high-intensity, and stable luminescence under the action of the electric field.

[0067] Referring to Figure 1 In some embodiments, the step of providing the high molecular polymer in a solid thin film form and filling the electroluminescent particles on the high molecular polymer, and embedding at least part of the electroluminescent particles on the surface of the high molecular polymer includes:

[0068] Mixing and dispersing the dispersion liquid containing the high molecular polymer with the electroluminescent particles to prepare a first dispersion liquid;

[0069] Coating the first dispersion liquid on a substrate;

[0070] Evaporating the dispersant in the first dispersion liquid coated on the substrate to form a preformed thin film;

[0071] Heating and curing the preformed thin film to make the high molecular polymer in a solid thin film form, and fill the electroluminescent particles on the high molecular polymer, and embed at least part of the electroluminescent particles on the surface of the high molecular polymer.

[0072] It can be understood that the coating method can be, for example but not limited to, spin coating, doctor blading, screen printing, etc. The above-mentioned coating can achieve the preliminary forming of the film, and a pre-formed film is formed.

[0073] In some embodiments, the coating method is spin coating. It can be understood that the spin coating speed, time, and other process conditions can be adjusted according to the thickness of the solid light-emitting material required, the viscosity of the first dispersion, the particle size of the electroluminescent particles, the mixing ratio of the polymer and the electroluminescent particles, and other factors.

[0074] Further, the mixture is coated on the substrate by spin coating, the spin coating speed is 300 rpm to 1100 rpm, and the spin coating time is 1 min to 3 min.

[0075] Further, the heating and curing conditions of the pre-formed film include a temperature of 250°C to 300°C and a holding time of 0.5 hours to 1 hour.

[0076] It can be understood that the dispersion containing the polymer can be self-prepared or commercially available.

[0077] Further, the method can further include a step of peeling the solid light-emitting material obtained after heating and curing from the substrate.

[0078] In some embodiments, the step of making the polymer into a solid film and filling the electroluminescent particles on the polymer, and making at least part of the electroluminescent particles inlaid on the surface of the polymer includes:

[0079] Dispersing the powdery polymer and the electroluminescent particles in a dispersant to prepare a second dispersion;

[0080] Filtering the second dispersion, collecting the residue and drying to prepare a solid mixture containing the polymer and the electroluminescent particles;

[0081] Hot pressing the solid mixture, or sequentially cold pressing and heating and curing the solid mixture, so that the polymer is made into a solid film, and the electroluminescent particles are filled on the polymer, and at least part of the electroluminescent particles are inlaid on the surface of the polymer.

[0082] Further, the hot pressing temperature is 10°C to 20°C higher than the viscous flow temperature of the polymer and lower than the decomposition temperature of the polymer.

[0083] Further, the hot pressing pressure is 3 MPa to 8 MPa.

[0084] Further, the high polymer is polyfluorinated ethylene propylene, and the hot-pressing forming condition includes a pressure of 3-8 MPa and a temperature of 295-305℃.

[0085] Further, the cold-pressing forming condition includes a pressure of 35-45 MPa and a normal temperature.

[0086] Further, the heating and curing treatment condition includes a temperature of 250-300℃ and a holding time of 0.5-1 hour.

[0087] Further, the dispersing agent is a non-polar volatile agent which does not react with the high polymer and the electroluminescent particles, such as, but not limited to, ethanol, petroleum ether, etc.

[0088] It can be understood that, in the processes of hot-pressing forming or cold-pressing forming, a mold with a specific size can be used for processing, and the thickness of the mold matches the preset product thickness of the solid-state luminescent material.

[0089] It can be understood that, in the process of preparing the solid-state luminescent material, in order to ensure the cleanliness of the product and avoid the interference of external impurities, the equipment and mold surface should be fully cleaned before any processing step such as coating, hot-pressing or cold-pressing.

[0090] No matter whether the coating, hot-pressing or cold-pressing process is used, the provided preparation method is simple in operation and wide in applicability.

[0091] In a third aspect, the present application also provides a luminescence method, including the following steps:

[0092] The liquid is contacted with the solid-state luminescent material in any of the embodiments of the first aspect.

[0093] It can be understood that, after the liquid is contacted with the solid-state luminescent material, the liquid can be static or continuously flowing, and when the liquid continuously flows, the solid-state luminescent material can continuously luminesce.

[0094] The solid-state luminescent material provided by the present application has strong stability, is easy to generate electricity after being contacted with the liquid, has large luminescence intensity, and has good repeatability, and truly realizes continuous and stable high-intensity luminescence of the liquid directly contacting the solid surface, which can be applied to the fields of utilizing liquid flowing energy, passive sensing display, etc. in production and life, and can also be applied to the scientific research fields of fluid boundary behavior and charge transfer in the solid-liquid contact process.

[0095] The present application is further described in detail by specific examples. The following examples are more specific, and it can be understood that in other examples, it is not limited thereto. In the following specific examples, the instruments, reagents, materials involved, if not specifically stated, are conventional instruments, reagents, materials existing in the prior art, which can be obtained through regular commercial channels. The experimental methods, detection methods, etc. involved in the following examples, if not specifically stated, are conventional experimental methods, detection methods existing in the prior art.

[0096] Electroluminescent particles: D512 electroluminescent powder from Shanghai Keyuan Optoelectronics Co., Ltd., the effective light-emitting component is zinc sulfide doped with copper (ZnS:Cu), the shell of the above zinc sulfide doped with copper is wrapped by aluminum oxide, and the average diameter is about 30 μm;

[0097] High molecular polymer: (1) polyperfluorinated ethylene propylene concentrated dispersion FR463 from Dongguan Zhan Yang High Molecular Material Co., Ltd.; (2) polyperfluorinated ethylene propylene powder with an average particle size of 20 μm from Dongguan Zhan Yang High Molecular Material Co., Ltd.

[0098] Example 1

[0099] Reference Figure 1 A preparation method of a solid light-emitting material, comprising the following steps:

[0100] 1. Using polyperfluorinated ethylene propylene as a high molecular polymer, a polyperfluorinated ethylene propylene concentrated dispersion is provided, and electroluminescent particles including zinc sulfide doped with copper are added to the dispersion, and stirred for 1 hour to ensure uniform dispersion of the light-emitting particles, forming a first dispersion containing the electroluminescent particles, the mass of the electroluminescent particles accounting for 30% of the sum of the mass of the electroluminescent particles and the mass of the high molecular polymer.

[0101] 3. After the glass slide is washed with acetone, it is fixed on the turntable of a spin coater, 0.2 mL of the first dispersion prepared in step 2 is added dropwise on the glass slide, and static spinning is performed at a rotation speed of 700 rpm for 2 min. After standing for half an hour, a preformed film is formed by volatilization of the first dispersion, and the glass slide containing the preformed film is transferred to a muffle furnace, heated and solidified at 285°C for half an hour, and then taken out and quickly cooled to room temperature.

[0102] Example 2

[0103] The same as example 1, the difference is that the rotation speed used in step 3 is different, specifically:

[0104] Static spinning is performed at a rotation speed of 1400 rpm for 2 min, respectively.

[0105] Example 3

[0106] The same as example 1, the difference is that the rotation speed of step 3 is different, specifically:

[0107] The static spin coating is carried out at the rotation speed of 300 rpm, 500 rpm, 900 rpm and 1100 rpm respectively for 2 min.

[0108] Example 4

[0109] The same as example 1, the difference is that the mass ratio of electroluminescent particles is different, specifically:

[0110] In the first dispersion liquid containing electroluminescent particles formed, the mass of electroluminescent particles accounts for 0%, 10%, 20%, 40% and 50% of the sum of the mass of electroluminescent particles and high molecular polymer respectively.

[0111] Example 5

[0112] 1. The polytetrafluoroethylene powder is used as the high molecular polymer, and the zinc sulfide doped copper is used as the effective light emitting component of the electroluminescent particles. The high molecular polymer powder and the electroluminescent particles are mixed in the dispersing agent ethanol according to the mass ratio of 7:3, stirred for 1 hour, and the second dispersion liquid is prepared.

[0113] 2. The second dispersion liquid is filtered, the filter residue is collected and dried, and a solid mixture containing high molecular polymer and electroluminescent particles is prepared.

[0114] 3. The mold is cleaned with acetone, alcohol and the like, the solid mixture is loaded into the mold after drying treatment, and the mold is fixed to the pressure plate of the press. The solid light emitting material is prepared by hot pressing treatment, and the hot pressing conditions are: pressure 5 MPa, temperature 300℃, holding time 10 minutes, and the thickness of the prepared solid light emitting material is 55μm.

[0115] Example 6

[0116] The same as example 5, the difference is that the hot pressing conditions and thickness of step 3 are different. Specifically:

[0117] The hot pressing conditions are: pressure 5 MPa, temperature 300℃, holding time 10 minutes, and the thickness of the prepared solid light emitting material is 30μm.

[0118] Comparative example 1

[0119] The traditional solid light emitting material of triboelectricity:

[0120] The electroluminescent particles were mixed into PDMS silicone component A, and then PDMS silicone component B was added in a mass ratio of 10:1 of component A to component B to form a solid-liquid mixture, and the total mass ratio of the electroluminescent particles to the PDMS silicone was 3:7. The solid-liquid mixture was cured at a temperature of 80°C for 2 hours to prepare a solid light-emitting material.

[0121] Comparative Example 2

[0122] A solid light-emitting material prepared according to Literature 2:

[0123] Two pieces of transparent polyperfluoroethylene propylene film, each having a thickness of 35 μm and a size of 7 cm x 7 cm, were provided. A PET film having a size of 7 cm x 7 cm and a thickness of 200 μm was provided, and a rectangular hollow frame having a size of 5 cm x 5 cm was formed by laser cutting. The PET film was fixed to one of the pieces of polyperfluoroethylene propylene film to form a mold. A mixture of electroluminescent particles containing zinc sulfide doped with copper and anhydrous ethanol was poured into the mold corresponding to the rectangular hollow frame, and a glass plate was used to level the mixture. The mixture was then dried and cured in an oven at a temperature of 130°C for 30 minutes to form an electroluminescent layer having a thickness of about 150 μm. The PET film was removed from the mold, and the electroluminescent layer was covered with another piece of polyperfluoroethylene propylene film to prepare a solid light-emitting material having a "electrification film-electroluminescent particle layer-electrification film layer" sandwich structure.

[0124] Comparative Example 3

[0125] A solid light-emitting material prepared according to Literature 1:

[0126] The electroluminescent particles containing zinc sulfide doped with copper were mixed with component A of Ecoflex 30 silicone, and then component B was added in a mass ratio of 1:1 of component A to component B to form a solid-liquid mixture. The total mass ratio of the electroluminescent particles to the Ecoflex 30 silicone was 3:7. The solid-liquid mixture was heated and cured in an oven at a temperature of 70°C for 20 minutes to form a solid light-emitting material.

[0127] Comparative Example 4

[0128] The procedure was substantially the same as in Example 5, except that no electroluminescent particles were added.

[0129] Comparative Example 5

[0130] The procedure was substantially the same as in Example 6, except that no electroluminescent particles were added.

[0131] As Figure 2 and Figure 3As shown in the figure, the surface morphology of the solid luminescent material prepared in Example 1 is observed by optical microscope, and it can be seen that the electroluminescent particles are inlaid on the surface of the polymer.

[0132] As shown in the figure, the surface morphology of the solid luminescent material prepared in Example 1 is observed by optical microscope, and it can be seen that the electroluminescent particles are inlaid on the surface of the polymer. Figures 4-7 As shown in the figure, the surface morphology of the solid luminescent material prepared in Example 1 is observed by optical microscope, and it can be seen that the electroluminescent particles are inlaid on the surface of the polymer.

[0133] Figure 8 As shown in the figure, the surface morphology of the solid luminescent material prepared in Example 1 is observed by optical microscope, and it can be seen that the electroluminescent particles are inlaid on the surface of the polymer.

[0134] Figure 9 As shown in the figure, the surface morphology of the solid luminescent material prepared in Example 1 is observed by optical microscope, and it can be seen that the electroluminescent particles are inlaid on the surface of the polymer.

[0135] The luminescent intensity of the solid luminescent material prepared in Example 1, Example 3 and Example 4 is tested, and the test method is as follows: a dropper with a fixed drop rate (about 1.67 Hz) is placed at 0.05 m above the solid luminescent material sample placed at an angle of 45°, and deionized water is used to contact the solid luminescent material to generate electricity and test the luminescent intensity, and the test results are shown in the figure. Figures 10-11

[0136] Figure 10 As shown in the figure, the luminescent intensity of the solid luminescent material prepared in Example 1 (spin coating speed 700 rpm) and Example 3 (spin coating speed 300 rpm, 500 rpm, 900 rpm, 1100 rpm) is tested, and the test results show that different spin coating speeds result in different luminescent intensities of the solid luminescent material, and the luminescent intensity is best at a speed of 700 rpm.

[0137] Figure 11 ​The results of the luminescent intensity test of the solid luminescent materials prepared by Example 1 (30% of the mass ratio of electroluminescent particles) and Example 4 (0%, 10%, 20%, 40%, and 50% of the mass ratio of electroluminescent particles) are shown. It can be seen from the test results that the luminescent intensity of the solid luminescent material is different due to the different mass ratios of electroluminescent particles, and the luminescent intensity is optimal when the mass ratio of electroluminescent particles to the sum of the mass of electroluminescent particles and the mass of the polymer is 30%.

[0138] The luminescent intensity of the solid luminescent materials prepared by Example 1, Comparative Example 1 to Comparative Example 3 was tested. The test method was as follows: a dropper with a fixed drop rate (about 1.67 Hz) was placed vertically at an angle of 45° above the solid luminescent material sample at a distance of 0.05 m, deionized water was used to contact the solid luminescent material to generate electricity (or frictionally contact to generate electricity) and make the material luminesce, the optical fiber probe was aimed at the luminescent position, and the optical fiber was connected to a single photon counter and a spectrometer for light intensity and spectrum detection. The test results are shown in Figures 12-13 .

[0139] As can be seen from Figure 12 , the luminescent spectra of Example 1, Comparative Example 1 to Comparative Example 3 were compared. It can be seen that the solid luminescent materials prepared by Example 1, Comparative Example 1 to Comparative Example 3 have similar luminescent spectra, indicating that the solid luminescent material prepared by Example 1 has electroluminescent effect.

[0140] As can be seen from Figure 13 , the contact electrification luminescence effect of the solid luminescent material prepared by Example 1 is significantly higher than that of Comparative Example 2 and Comparative Example 3, and is closer to the luminescence effect of the traditional frictionally electrified solid luminescent material of Comparative Example 1.

[0141] In addition, Example 1 continuously added droplets for 2 hours without any pre-treatment, the total number of droplets exceeded 12000, the surface of the solid luminescent material did not change, and it still emitted light normally, and the brightness remained stable. Comparative Example 1 and Comparative Example 3 needed to be rubbed on the solid luminescent material in advance, then a droplet was added to emit light once, and then the next droplet was added. If the solid luminescent material was not rubbed again, it could not emit light again. After continuously adding droplets to Comparative Example 2 for more than 5000 times, a gap appeared between the layers, and the luminescent brightness decreased after adding droplets. After the solid luminescent material of Comparative Example 2 was placed indoors for two days, the overall structure became loose, the layers separated, and the two FEP films had to be re-bonded to re-achieve droplet luminescence.

[0142] The technical features of the above-described embodiments can be combined in any manner. To make the description concise, not all possible combinations of the technical features in the above-described embodiments are described, however, as long as the combinations of the technical features do not contradict, they should be considered within the scope of the present disclosure.

[0143] The above embodiments only express several implementation manners of the present application, which are described in a more specific and detailed manner, but cannot be understood as a limitation on the patent scope of the present application. It should be noted that, for those skilled in the art, several modifications and improvements can be made without departing from the concept of the present application, which all belong to the protection scope of the present application. Therefore, the protection scope of the present application patent should be subject to the appended claims.

Claims

1. A solid-state luminescent material, characterized in that, include: A polymer, wherein the polymer is in the form of a solid film and is capable of being electrically charged; as well as Electroluminescent particles, wherein the electroluminescent particles are filled on the polymer, and at least some of the electroluminescent particles are embedded on the surface of the polymer; the thickness of the solid luminescent material is 1 to 2 times the diameter of the electroluminescent particles; The mass of the electroluminescent particles accounts for 25% to 35% of the sum of the mass of the polymer and the electroluminescent particles; The polymers include one or more of the following: perfluorinated ethylene propylene, polytetrafluoroethylene, polyvinylidene fluoride, ethylene-tetrafluoroethylene copolymer, polyvinyl chloride, polyethylene, and nylon.

2. The solid-state luminescent material according to claim 1, characterized in that, The electroluminescent particles include one or more of zinc sulfide-doped copper, zinc sulfide-doped manganese, strontium sulfide-doped copper, and strontium sulfide-doped cerium.

3. A method for preparing a solid-state luminescent material as described in claim 1 or 2, characterized in that, Includes the following steps: A contactable electrostatic polymer is provided, wherein the polymer is in the form of a solid film, and electroluminescent particles are filled on the polymer, such that at least a portion of the electroluminescent particles are embedded in the surface of the polymer.

4. The method for preparing the solid-state luminescent material according to claim 3, characterized in that, The steps of forming the polymer into a solid film, filling the polymer with electroluminescent particles, and embedding at least some of the electroluminescent particles into the surface of the polymer include: The dispersion containing the polymer is mixed and dispersed with the electroluminescent particles to prepare a first dispersion. The first dispersion is coated onto the substrate; The dispersant in the first dispersion liquid coated on the substrate is evaporated to form a pre-formed film; The pre-formed film is heated and cured to make the polymer solid film, and the electroluminescent particles are filled on the polymer, with at least some of the electroluminescent particles embedded on the surface of the polymer.

5. The method for preparing the solid-state luminescent material according to claim 4, characterized in that, The first dispersion was coated onto the substrate by spin coating at a speed of 300 rpm to 1100 rpm for a time of 1 min to 3 min.

6. The method for preparing the solid-state luminescent material according to claim 3, characterized in that, The steps of forming the polymer into a solid film, filling the polymer with electroluminescent particles, and embedding at least some of the electroluminescent particles into the surface of the polymer include: The powdered polymer and the electroluminescent particles are dispersed in a dispersant to prepare a second dispersion. The second dispersion is filtered, the filter residue is collected and dried to prepare a solid mixture containing the polymer and the electroluminescent particles; The solid mixture is hot-pressed or cold-pressed and then heated and cured sequentially to form a solid film, and the electroluminescent particles are filled on the polymer, with at least some of the electroluminescent particles embedded on the surface of the polymer.

7. A method for emitting light, characterized in that, The process includes the following steps: contacting the liquid with the solid luminescent material as described in claim 1 or 2.

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